Insecticidal (dihalopropenyl) phenylalkyl substituted dihydrobenzofuran and dihydrobenzopyran derivatives

ABSTRACT

Insecticidal (dihalopropenyl) phenylalkyl substituted dihydrobenzofuran and dihydrobenzopyran derivatives of Formula I are disclosed. These compounds provide unexpected insecticidal activity across a spectrum of insect pests combined with desirable physical properties including improved photostability.  
                 
 
     wherein x and y are integers independently selected from 0 or 1; and B is a bridging group 
     *—(CR 16 R 17 ) q —(CR 18 R 19 ) r —(CR 20 R 21 ) s —L t —(CR 22 R 23 ) u —(CR 24 R 25 ) v —(CR 26 R 27 ) w —, 
     where the asterisk denotes attachment at A; and q, r, s, u, v and w are integers independently selected from 0, 1 and 2; and t is an integer selected from 0 and 1. A, D, E, G, M, R through R 11 , and R 16  through R 27 , inclusively, are fully described herein. In addition, compositions comprising an insecticidally effective amount of at least one compound of formula I and methods of controlling insects by applying said compositions to a locus where insects are present or are expected to be present are also disclosed.

[0001] This application claims the benefit of U.S. ProvisionalApplication No. 60/466,674, filed Apr. 30, 2003.

FIELD OF THE INVENTION

[0002] The present invention relates to novel compounds and their use incontrolling insects and acarids. In particular, it pertains to(dihalopropenyl) phenylalkyl substituted dihydrobenzofuran anddihydrobenzopyran derivatives and agriculturally acceptable saltsthereof, compositions containing them and methods for their use incontrolling insects and acarids.

BACKGROUND OF THE INVENTION

[0003] It is well known that insects can cause significant damage, notonly to crops grown in agriculture, such as wheat, corn, soybeans,potatoes, and cotton but also, for example, to structures and turf wherethe damage is caused by soil-borne insects, such as termites and whitegrubs. Such damage may result in the loss of millions of dollars ofvalue associated with a given crop, turf or structure. Insecticides andacaricides are useful for controlling such insects and acarids.

[0004] A number of patents and publications disclose a variety ofdihalopropene compounds that are reported to be insecticidally andacaricidally active. For example, U.S. Pat. No. 5,922,880 disclosescertain dihalopropene compounds containing optionally substitutedheterocyclic ring groups for use as insecticides and acaricides.Examples of the heterocyclic ring in the optionally substitutedheterocyclic ring group are isoxazole, thiazole, 1,3,4-thiadiazole,pyrrole, furan, thiophene, pyrazole, imidazole, 1,2,3-triazole,1,2,4-triazole, 1,2,3,4-tetrazole, pyridine, pyridazine, pyrimidine,pyrazine, 1,2,4-triazine, 1,3,5-triazine, indole, benzofuran,thianaphthalene, indazole, benzimidazole, benzotriazole, benzisoxazole,benzoxazole, benzothiazole, quinoline, isoquinoline, quinoxaline,quinazole, piperidine, piperazine, tetrahydrofuran, tetrahydropyran,pyrazoline, phthalimnide, dioxane, dioxolane, and benzodioxolane (Column3, lines 15-25).

[0005] Insecticides containing dihydrobenzofuranyl substituents are alsoknown in the art. See, in this regard, U.S. Pat. Nos. 3,474,170 and3,474,171 which disclose dihydrobenzofuranyl esters of carbamic acids.

[0006] In addition to activity against target pests a commerciallyviable pesticide needs to satisfy a number of additional criteriaincluding, inter alia, production costs, environmental impact, mammaliantoxicity, lack of undesirable effects on target crops and certainphysical characteristics. Desirable physical characteristics for acompound to be used in an outdoor field environment include inter alia,photochemical stability under field conditions. Photostable insecticidesand acaricides, i.e., those which do not break down or degrade whenexposed to sunlight, are advantageous in that they provide long-terminsecticidal and acaricidal activity, which increases the effectivenessof the active compound.

[0007] Efficacy problems associated with pesticides that have limitedphotostability are well known. For example, Clough et al. (Fungicidalβ-Methoxyacrylates; Synthesis and Chemistry of Agrochemicals, ACSSymposium Series 504, Chapter 34 (1992)) describes disappointingfungicidal activity of certain compounds when tested in light, andefforts to synthesize fungicides with greater photostability. In anotherexample, Shiokawa, et al. (Chloronicotinyl Insecticides: Development ofImidacloprid; Eighth International Congress of PesticideChemistry-Options 2000, ACS Publication 1995) describes the wavelengthsof sunlight that reach the earth's surface that can causephoto-degradation of certain compounds such as nitromethyleneinsecticides and other compounds.

[0008] Accordingly, there is a continuing demand for new insecticidesand acaricides that are safe, more effective e,g, more photostable, andless costly to prepare on a commercial scale.

SUMMARY OF THE INVENTION

[0009] In accordance with the present invention, it has now been foundthat certain dihalopropenyl phenylalkyl compounds containing asubstituted benzo fused heterocycle wherein the heterocycle is either asaturated 5 or 6 membered ring containing one oxygen atom (i.e., adihydrobenzofuran or a dihydrobenzopyran) are active in the control ofinsects and acarids. Additionally, these compounds are unexpectedlyphotochemically stable. The novel compounds are represented by thefollowing general formula I:

[0010] wherein

[0011] R and R³ are independently selected from hydrogen, halogen,hydroxy, (C₁-C₃)alkyl, (C₃-C₆)cycloalkyl, (C₂-C₅)alkenyl,(C₂-C₅)alkynyl, halo(C₁-C₃)alkyl, (C₁-C₃)alkoxy, halo(C₁-C₃)alkoxy,(C₁-C₃)alkylthio, halo(C₁-C₃)alkylthio, (C₁-C₃)alkylsulfonyl,halo(C₁-C₃)alkylsulfonyl, cyano, nitro; optionally substituted aminowherein the optional substituent is selected from (C₁-C₄)alkyl,(C₁-C₃)alkylcarbonyl and (C₁-C₃)alkoxycarbonyl; optionally substitutedimidazolyl, optionally substituted imidazolinyl, optionally substitutedoxazolinyl, optionally substituted oxazolyl, optionally substitutedoxadiazolyl, optionally substituted thiazolyl, optionally substitutedpyrazolyl, optionally substituted triazolyl, optionally substitutedfuranyl, optionally substituted tetrahydrofuranyl, optionallysubstituted dioxolanyl, optionally substituted dioxanyl, —C(═J)—K, and—C(R¹²)—Q—R¹³, wherein the optional substituent is selected from(C₁-C₄)alkyl, halo(C₁-C₄)alkyl, (C₁-C₄)alkoxy,(C₁-C₄)alkoxy(C₁-C₄)alkyl, (C₃-C₆)cycloalkyl, (C₂-C₅)alkenyl,(C₂-C₅)alkynyl, cyano, nitro and aryl;

[0012] where

[0013] J is selected from O, S, NR¹⁴, and NOR¹⁴, where R¹⁴ is hydrogen,(C₁-C₄)alkyl, halo(C₁-C₄)alkyl, aryl and aryl(C₁-C₄)alkyl;

[0014] K is selected from hydrogen, (C₁-C₃)alkyl, halo(C₁-C₃)alkyl,(C₁-C₃)alkoxy, (C₁-C₃)alkylamino and di(C₁-C₃)alkylamino;

[0015] Q is selected from O, S, and NR¹⁴, where R¹⁴ is as previouslydescribed;

[0016] R¹² and R¹³ are independently selected from hydrogen,(C₁-C₄)alkyl and halo(C₁-C₄)alkyl, and R¹² and R¹³ may be taken togetherwith —T(CHR¹⁴)_(m)—, where m is an integer of 2 to 4; T is selected fromO, S, and NR¹⁴, where R¹⁴ is as previously described;

[0017] R¹ and R² are independently selected from hydrogen, halogen and(C₁-C₃)alkyl;

[0018] R⁴ is hydrogen;

[0019] R⁵'s are independently selected from halogen;

[0020] E is selected from CH₂, O, S and NR¹⁵ where R¹⁵ is selected fromhydrogen, (C₁-C₃)alkyl, (C₁-C₃)alkoxy(C₁-C₃)alkyl, aryl(C₁-C₃)alkyl,(C₂-C₄)alkenyl(C₁-C₃)alkyl, halo(C₂-C₄)alkenyl(C₁-C₃)alkyl,di(C₁-C₃)alkylphosphonate, formyl, (C₁-C₃)alkylcarbonyl,halo(C₁-C₃)alkylcarbonyl, (C₁-C₃)alkoxy(C₁-C₃)alkylcarbonyl,arylcarbonyl and (C₁-C₃)alkylsulfonyl;

[0021] G is selected from O, S, CH₂O* and (CH₂)_(n) where the asteriskdenotes attachment to E, and n is an integer selected from 1 and 2provided that E and G are not simultaneously O or S,

[0022] x is an integer selected from 0 or 1; and when x is 1,

[0023] A is selected from O, S(O)_(p) and —NR¹⁵, where p is an integerselected from 0, 1 and 2, and R¹⁵ is as previously described;

[0024] B is a bridging group,

*—(CR¹⁶R¹⁷)_(q)—(CR¹⁸R¹⁹)_(r)—(CR²⁰R²¹)_(s)—L_(t)—(CR²²R²³)_(u)—(CR²⁴R²⁵)_(v)—(CR²⁶R²⁷)_(w)—,

[0025] where

[0026] the asterisk denotes attachment at A; q, r, s, u, v and w areintegers independently selected from 0, 1 and 2;

[0027] and

[0028] when q, r, s, u, v or w are 1 or 2,

[0029] R¹⁶ through R²⁷, inclusively, are independently selected fromhydrogen, (C₁-C₃)alkyl, halo(C₁-C₃)alkyl, (C₁-C₃)alkoxy(C₁-C₃)alkyl, and(C₃-C₆)cycloalkyl;

[0030] t is an integer selected from 0 or 1; and

[0031] when t is 1,

[0032] L is selected from CH═CH; O, S(O)_(p); OS(O)₂, S(O)₂O, NR²⁸;N(oxide)R²⁸; NR²⁸SO₂; NR²⁸C(═O)NR²⁹; Si(CH₃)₂; C(═O), OC(═O), NHC(═O);ON═CH; HC═NO; C(═O)O; C(═O)NH; C(═NOR¹⁴) and [CR³⁰R³¹]_(z), where p isas previously described, R²⁸ and R²⁹ are independently selected fromhydrogen, (C₁-C₃)alkyl, (C₁-C₃)alkylsulfonyl, (C₁-C₃)alkylcarbonyl,(C₂-C₅)alkenyl, and (C₂-C₅)alkynyl; z is an integer selected from 1 or2; and R³⁰ and R³¹ are independently selected from hydrogen and(C₁-C₃)alkyl;

[0033] y is an integer selected from 0 or 1; and when y is 1,

[0034] D is selected from O; S(O)_(p); and NR¹⁵, where p and R¹⁵ are aspreviously described, wherein D is attached to the benzo-fused ringmoiety set forth in formula I at any one of the positions designated 1-,2-, 3- or 4-:

[0035] R⁶, R⁷, R⁸ and R⁹ are independently selected from hydrogen,halogen, (C₁-C₄)alkyl, (C₃-C₆)cycloalkyl, (C₂-C₅)alkenyl,(C₂-C₅)alkynyl, halo(C₁-C₄)alkyl, (C₁-C₄)alkoxy, halo(C₁-C₄)alkoxy,(C₁-C₄)alkylthio, halo(C₁-C₄)alkylthio, (C₁-C₄)alkylsulfonyl,halo(C₁-C₄)alkylsulfonyl, cyano, nitro, aryl, alkylcarbonylamino,arylcarbonylamino, and (C₁-C₄)alkoxycarbonylamino;

[0036] R¹⁰ and R¹¹ are independently selected from hydrogen, halogen,hydroxyl, alkyl, haloalkyl, alkoxy,

[0037] or

[0038] R¹⁰ and R¹¹ taken together are ═O forming a carbonyl group; or—OCH₂CH₂O— or —SCH₂CH₂S— forming a ketal or a thioketal group; or NOR¹⁵forming an oxime, where R¹⁵ is as previously described;

[0039] M is selected from *C(R³²R³³) and *C(R³²R³³)C(R³⁴R³⁵) where theasterisk indicates attachment to O and wherein R³² through R³⁵

[0040] are selected from halogen, (C₁-C₄)alkyl,(C₁-C₄)alkoxy(C₁-C₄)alkyl, and halo(C₁-C₄)alkyl;

[0041] and

[0042] agriculturally acceptable salts thereof.

[0043] Preferred compounds are the substituted dihydrobenzofuranderivatives—i.e., those where M is *C(R³²R³³) and wherein R³² and R³³are the same and are selected from alkyl, particularly methyl, and halo,particularly fluoro.

[0044] The present invention also includes compositions containing aninsecticidally effective amount of at least one compound of formula I,and optionally, an effective amount of at least one second compound,with at least one insecticidally compatible carrier.

[0045] The present invention also includes methods of controllinginsects, in an area where control is desired, which comprise applying aninsecticidally effective amount of the above composition to the locus ofcrops, or other areas where insects are present or are expected to bepresent.

DETAILED DESCRIPTION OF THE INVENTION

[0046] The present invention relates to certain new and usefulinsecticidal and acaricidal compounds, namely dihalopropenyl phenylalkylsubstituted dihydrobenzofurans or dihydrobenzopyrans (hereinafter termed“compounds of formula I”) as depicted in general formula I:

[0047] wherein

[0048] R and R³ are independently selected from hydrogen, halogen,hydroxy, (C₁-C₃)alkyl, (C₃-C₆)cycloalkyl, (C₂-C₅)alkenyl,(C₂-C₅)alkynyl, halo(C₁-C₃)alkyl, (C₁-C₃)alkoxy, halo(C₁-C₃)alkoxy,(C₁-C₃)alkylthio, halo(C₁-C₃)alkylthio, (C₁-C₃)alkylsulfonyl,halo(C₁-C₃)alkylsulfonyl, cyano, nitro; optionally substituted aminowherein the optional substituent is selected from (C₁-C₄)alkyl,(C₁-C₃)alkylcarbonyl and (C₁-C₃)alkoxycarbonyl; optionally substitutedimidazolyl, optionally substituted imidazolinyl, optionally substitutedoxazolinyl, optionally substituted oxazolyl, optionally substitutedoxadiazolyl, optionally substituted thiazolyl, optionally substitutedpyrazolyl, optionally substituted triazolyl, optionally substitutedfuranyl, optionally substituted tetrahydrofuranyl, optionallysubstituted dioxolanyl, optionally substituted dioxanyl, —C(═J)—K, and—C(R¹²)—Q—R¹³, wherein the optional substituent is selected from(C₁-C₄)alkyl, halo(C₁-C₄)alkyl, (C₁-C₄)alkoxy,(C₁-C₄)alkoxy(C₁-C₄)alkyl, (C₃-C₆)cycloalkyl, (C₂-C₅)alkenyl,(C₂-C₅)alkynyl, cyano, nitro and aryl;

[0049] where

[0050] J is selected from O, S, NR¹⁴, and NOR¹⁴, where R¹⁴ is hydrogen,(C₁-C₄)alkyl, halo(C₁-C₄)alkyl, aryl and aryl(C₁-C₄)alkyl;

[0051] K is selected from hydrogen, (C₁-C₃)alkyl, halo(C₁-C₃)alkyl,(C₁-C₃)alkoxy, (C₁-C₃)alkylamino and di(C₁-C₃)alkylamino;

[0052] Q is selected from O, S, and NR¹⁴, where R¹⁴ is as previouslydescribed;

[0053] R¹² and R¹³ are independently selected from hydrogen,(C₁-C₄)alkyl and halo(C₁-C₄)alkyl, and R¹² and R¹³ may be taken togetherwith —T(CHR¹⁴)_(m)—, where m is an integer of 2 to 4; T is selected fromO, S, and NR¹⁴, where R¹⁴ is as previously described;

[0054] R¹ and R² are independently selected from hydrogen, halogen and(C₁-C₃)alkyl;

[0055] R⁴ is hydrogen;

[0056] R⁵'s are independently selected from halogen;

[0057] E is selected from CH₂, O, S and NR¹⁵ where R¹⁵ is selected fromhydrogen, (C₁-C₃)alkyl, (C₁-C₃)alkoxy(C₁-C₃)alkyl, aryl(C₁-C₃)alkyl,(C₂-C₄)alkenyl(C₁-C₃)alkyl, halo(C₂-C₄)alkenyl(C₁-C₃)alkyl,di(C₁-C₃)alkylphosphonate, formyl, (C₁-C₃)alkylcarbonyl,halo(C₁-C₃)alkylcarbonyl, (C₁-C₃)alkoxy(C₁-C₃)alkylcarbonyl,arylcarbonyl and (C₁-C₃)alkylsulfonyl;

[0058] G is selected from O, S, CH₂O* and (CH₂)_(n) where the asteriskdenotes attachment to E, and n is an integer selected from 1 and 2provided that E and G are not simultaneously O or S,

[0059] x is an integer selected from 0 or 1; and when x is 1,

[0060] A is selected from O, S(O)_(p) and —NR⁵, where p is an integerselected from 0, 1 and 2, and R¹⁵ is as previously described;

[0061] B is a bridging group,

*—(CR¹⁶R¹⁷)_(q)—(CR¹⁸R¹⁹)_(r)—(CR²⁰R²¹)_(s)—L_(t)—(CR²²R²³)_(u)—(CR²⁴R²⁵)_(v)—(CR²⁶R²⁷)_(w)—,

[0062] where

[0063] the asterisk denotes attachment at A; q, r, s, u, v and w areintegers independently selected from 0, 1 and 2;

[0064] and

[0065] when q, r, s, u, v or w are 1 or 2,

[0066] R¹⁶ through R²⁷, inclusively, are independently selected fromhydrogen, (C₁-C₃)alkyl, halo(C₁-C₃)alkyl, (C₁-C₃)alkoxy(C₁-C₃)alkyl, and(C₃-C₆)cycloalkyl;

[0067] t is an integer selected from 0 or 1; and

[0068] when t is 1,

[0069] L is selected from CH═CH; O, S(O)_(p); OS(O)₂, S(O)₂O, NR²⁸;N(oxide)R²⁸; NR²⁸SO₂; NR²⁸C(═O)NR²⁹; Si(CH₃)₂; C(═O), OC(═O), NHC(═O);ON═CH; HC═NO; C(═O)O; C(═O)NH; C(═NOR¹⁴) and [CR³⁰R³¹]_(z), where p isas previously described, R²⁸ and R²⁹ are independently selected fromhydrogen, (C₁-C₃)alkyl, (C₁-C₃)alkylsulfonyl, (C₁-C₃)alkylcarbonyl,(C₂-C₅)alkenyl, and (C₂-C₅)alkynyl; z is an integer selected from 1 or2; and R³⁰ and R³¹ are independently selected from hydrogen and(C₁-C₃)alkyl;

[0070] y is an integer selected from 0 or 1; and when y is 1,

[0071] D is selected from O; S(O)_(p); and NR¹⁵, where p and R¹⁵ are aspreviously described, wherein D is attached to the benzo-fused ringmoiety set forth in formula I at any one of the positions designated 1-,2-, 3- or 4-:

[0072] R⁶, R⁷, R⁸ and R⁹ are independently selected from hydrogen,halogen, (C₁-C₄)alkyl, (C₃-C₆)cycloalkyl, (C₂-C₅)alkenyl,(C₂-C₅)alkynyl, halo(C₁-C₄)alkyl, (C₁-C₄)alkoxy, halo(C₁-C₄)alkoxy,(C₁-C₄)alkylthio, halo(C₁-C₄)alkylthio, (C₁-C₄)alkylsulfonyl,halo(C₁-C₄)alkylsulfonyl, cyano, nitro, aryl, alkylcarbonylamino,arylcarbonylamino, and (C₁-C₄)alkoxycarbonylamino;

[0073] R¹⁰ and R¹¹ are independently selected from hydrogen, halogen,hydroxyl, alkyl, alkoxy,

[0074] or

[0075] R¹⁰ and R¹¹ taken together are ═O forming a carbonyl group;OCH₂CH₂O or SCH₂CH₂S forming a ketal or a thioketal group; or NOR¹⁵forming an oxime, where R¹⁵ is previously described;

[0076] M is selected from *C(R³²R³³) and *C(R³²R³³)C(R³⁴R³⁵) where theasterisk indicates attachment to O and wherein R³² through R³⁵

[0077] are selected from, halogen, (C₁-C₄)alkyl,(C₁-C₄)alkoxy(C₁-C₄)alkyl, and

[0078] halo(C₁-C₄)alkyl,

[0079] and

[0080] agriculturally acceptable salts thereof.

[0081] Preferred compounds of formula I are those where

[0082] R and R³ are independently selected from halogen and(C₁-C₃)alkyl;

[0083] R¹, R², and R⁴ are hydrogen;

[0084] R⁵'s are independently selected from chlorine, bromine, andfluorine;

[0085] E is O;

[0086] G is (CH₂)_(n), where n is 1;

[0087] x is 1, and A is O;

[0088] and

[0089] when q, r, s, u, v and w are 1 or 2, R¹⁶ through R²⁷,inclusively, are hydrogen;

[0090] t is 0 or 1,

[0091] and

[0092] when t is 1,

[0093] L is selected from O, OC(═O), NHC(═O), ON═CH, and CH═NO;

[0094] y is 1,

[0095] and

[0096] D is selected from O; S(O)_(p); and NR¹⁵, where p is 0, and R¹⁵is selected from hydrogen, (C₁-C₃)alkyl, aryl(C₁-C₃)alkyl,(C₂-C₄)alkenyl(C₁-C₃)alkyl, and halo(C₂-C₄)alkenyl(C₁-C₃)alkyl, whereinD is attached to the benzo-fused moiety set forth in formula I at theposition designated 1 or 4;

[0097] R⁶, R⁷, R⁸ and R⁹ are independently selected from hydrogen,halogen, halo(C₁-C₄)alkyl and nitro;

[0098] R¹⁰ and R¹¹ are hydrogen, or R¹⁰ and R¹¹ taken together are ═Oforming a carbonyl group;

[0099] and

[0100] M is C(R³²R³³), where R³² and R³³ are independently (C₁-C₄)alkyl.

[0101] Particularly preferred compounds are those of Formula II

[0102] wherein:

[0103] R¹ and R² are hydrogen;

[0104] R and R³ are selected from halogen, especially chlorine, and (C₁to C₃)alkyl, especially methyl;

[0105] R⁵ is halogen, especially chlorine or bromine;

[0106] R⁷, R⁸ and R⁹ are hydrogen, halogen, haloalkyl or nitro,especially hydrogen;

[0107] R¹⁰ and R¹¹ are hydrogen or taken together are ═O, especiallyhydrogen;

[0108] B is (CH2)n where n is an integer from 2 to 6; and

[0109] M is C(R³²R³³) where R³²R³³ are halogen or (C₁-C₄)alkyl,especially C₁ to C₄ alkyl and most especially methyl,

[0110] Most particularly preferred compounds of formula II are thosewhere R, R³, and R⁵ are chlorine; n is 3 or 4 and R³² and R³³ are C₁ toC₄ alkyl. An especially preferred compound is that having the structureof formula III below:

[0111] namely5-(3,3-dichloroprop-2-enyloxy)-2-[4-(2,2-dimethyl(2,3-dihydrobenzo[2,3-b]furan-7-yloxy))butoxy]-1,3-dichlorobenzene.

[0112] In addition, in certain cases the compounds of the presentinvention may possess asymmetric centers, which can give rise to opticalenantiomorphs and diastereomers. The compounds may exist in two or moreforms, i.e., polymorphs, which are significantly different in physicaland chemical properties. The compounds of the present invention may alsoexist as tautomers, in which migration of a hydrogen atom within themolecule results in two or more structures, which are in equilibrium.The compounds of the present invention may also possess acidic or basicmoieties, which may allow for the formation of agriculturally acceptablesalts or agriculturally acceptable metal complexes.

[0113] This invention includes the use of such enantiomorphs,polymorphs, tautomers, salts and metal complexes. Agriculturallyacceptable salts and metal complexes include, without limitation, forexample, ammonium salts, the salts of organic and inorganic acids, suchas hydrochloric acid, sulfonic acid, ethanesulfonic acid,trifluoroacetic acid, methylbenzenesulfonic acid, phosphoric acid,gluconic acid, pamoic acid, and other acid salts, and the alkali metaland alkaline earth metal complexes with, for example, sodium, potassium,lithium, magnesium, calcium, and other metals.

[0114] The methods of the present invention comprise causing aninsecticidally effective amount of a compound of formula I to beadministered to insects in order to kill or control the insects.Preferred insecticidally effective amounts are those that are sufficientto kill the insect. It is within the scope of the present invention tocause a compound of formula I to be present within insects by contactingthe insects with a derivative of that compound, which derivative isconverted within the insect to a compound of formula I. This inventionincludes the use of such compounds, which are referred to aspro-insecticides.

[0115] Another aspect of the present invention relates to compositionscontaining an insecticidally effective amount of at least one compoundof formula I.

[0116] Another aspect of the present invention relates to compositionscontaining an insecticidally effective amount of at least one compoundof formula I, and an effective amount of at least one second compound.

[0117] Another aspect of the present invention relates to methods ofcontrolling insects by applying an insecticidally effective amount of acomposition as set forth above to a locus of crops such as, withoutlimitation, cereals, cotton, vegetables, and fruits, or other areaswhere insects are present or are expected to be present.

[0118] The present invention also includes the use of the compounds andcompositions set forth herein for control of non-agricultural insectspecies, for example, dry wood termites and subterranean termites; aswell as for use as pharmaceutical agents. In the field of veterinarymedicine, the compounds of the present invention are expected to beeffective against certain endo- and ecto-parasites, such as insects andworms, which prey on animals. Examples of such animal parasites include,without limitation, Gastrophilus spp., Stomoxys spp., Trichodectes spp.,Rhodnius spp., Ctenocephalides canis, and other species.

[0119] As used in this specification and unless otherwise indicated thesubstituent terms “alkyl” and “alkoxy”, used alone or as part of alarger moiety, includes straight or branched chains of at least one ortwo carbon atoms, as appropriate to the substituent, and preferably upto 12 carbon atoms, more preferably up to ten carbon atoms, mostpreferably up to seven carbon atoms. The term “alkenyl” and “alkynyl”used alone or as part of a larger moiety, includes straight or branchedchains of at least two carbon atoms containing at least onecarbon-carbon double bond or triple bond, and preferably up to 12 carbonatoms, more preferably up to ten carbon atoms, most preferably up toseven carbon atoms. The term “aryl” refers to an aromatic ringstructure, including fused rings, having six to ten carbon atoms, forexample, phenyl or naphthyl. The term “heteroaryl” refers to an aromaticring structure, including fused rings, in which at least one of theatoms is other than carbon, for example, without limitation, sulfur,oxygen, or nitrogen. The term “GC analysis” refers to gaschromatographic analysis of; while the term “TLC analysis” refers tothin layer chromatographic analysis of, for example a reaction mixture.The term “HPLC” refers to high pressure liquid chromatography, as itrelates to, for example a method of separating components from areaction mixture. The term “DMF” refers to N,N-dimethylformamide. Theterm “THF” refers to tetrahydrofuran. The term “halogen” or “halo”refers to fluorine, bromine, iodine, or chlorine. The term “ambienttemperature” or “room temperature” often abbreviated as “RT”, forexample, in reference to a chemical reaction mixture temperature, refersto a temperature in the range of 20° C. to 30° C. The term“insecticidal” or “acaricidal”, “insecticide” or “acaricide” refers to acompound of the present invention, either alone or in admixture with atleast one of a second compound, or with at least one compatible carrier,which causes the destruction or the inhibition of action of insects oracarids. The term “independently selected from” as set forth above andin the claims section of the present specification refers to thepossibility that moieties, for example the R⁵'s, may be the same or theymay be different within the group that the selection is made.

[0120] The substituted arylalkene derivatives of formula I can besynthesized by methods that are individually known to one skilled in theart from available intermediate compounds.

[0121] Scheme 1 below illustrates a general procedure for synthesizingsubstituted arylalkene compounds of formula I, inter alia, where, forexample, R¹, R², R⁴, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are hydrogen; R, R³ andR⁵'s are chloro; M is —C(R³²R³³)—, where R³² and R³³ are methyl; q, r, sand u are 1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹ R²⁰, R²¹, R²² and R²³ arehydrogen, t, v and w are 0; x and y are 1; A, D and E are O, where D isattached to the benzo-fused ring at the position designated as 1; and Gis (CH₂)_(n) where n is 1;

[0122] In a first step as depicted in Scheme 1, an appropriatelysubstituted phenol, for example, the known compound2,6-dichloro-4-phenylmethoxyphenol, was reacted under basic conditionswith a haloalkane derivative of a desired carbon chain length, forexample 1-bromo-4-chlorobutane, to attach the bridging group B, therebyaffording the corresponding1,3-dichloro-2-(4-chlorobutoxy)-5-(phenylmethoxy)benzene (A).Intermediate (A) was then reacted under basic conditions with, forexample, the known compound 2,2-dimethyl-2,3-dihydrobenzo[b]furan-7-ol,to attach moiety D, as well as the benzo-fused ring, affording thecorresponding2-[4-(2,2-dimethyl-(2,3-dihydrobenzo[2,3-b]furan-7-yloxy))butoxy]-1,3-dichloro-5-(phenylmethoxy)benzene(B). Intermediate (B), for example2-[4-(2,2-dimethyl-(2,3-dihydrobenzo[2,3-b]furan-7-yloxy))butoxy]-1,3-dichloro-5-(phenylmethoxy)benzene,as set forth above, was then reduced with hydrogen gas in the presenceof a catalyst, for example 10% palladium on carbon, providing thecorresponding4-[4-(2,2-dimethyl(2,3-dihydrobenzo[2,3-b]furan-7-yloxy))butoxy]-3,5-dichlorophenol(C). Intermediate (C) was then reacted under basic conditions with, forexample, 1,1,1,3-tetrachloropropane, which simultaneouslydehydrohalogenates, thereby introducing the moiety —E—G—C(R⁴)═C(R⁵)(R⁵)into the molecule to provide Compound 12, a novel compound of formula I.Example 1 set forth below, provides a detailed method to how Compound 12shown in Scheme 1 was prepared.

[0123] Scheme 2 below illustrates a general procedure for synthesizingsubstituted arylalkene derivatives of formula I, inter alia, where, forexample, R¹, R², R⁴, R⁷, R⁸ and R⁹ are hydrogen; R¹⁰ and R¹¹ are takentogether with O to form a carbonyl group; R, R³ and R⁵'s are chloro; Mis —C(R³²R³³)—, where R³² and R³³ are methyl; q, r, s and u are 1, whereR¹⁶, R¹⁷, R¹⁸, R¹⁹ R²⁰, R²¹, R²² and R²³ are hydrogen, t, v and w are 0;x and y are 1; A, D and E are O, where D is attached to the benzo-fusedring at the position designated as 1; and G is (CH₂)_(n) where n is 1;

[0124] As depicted in Scheme 2, certain compounds of the presentinvention, i.e., compounds of formula I, may be further reacted toprovide additional compounds of formula I. For example, Compound 12 wasoxidized with potassium persulfate and copper sulfate pentahydrate,affording the corresponding ketone derivative (Compound 36), where R¹⁰and R¹¹ are taken together with O to form a carbonyl group. Example 2set forth below, provides a detailed method to how Compound 36 shown inScheme 2 was prepared.

[0125] Scheme 3 below illustrates a general procedure for synthesizingsubstituted arylalkene compounds of formula I, where, for example, R¹,R², R⁴, R¹⁰ and R¹¹ are hydrogen; R⁷, R⁸ or R⁹ may be a substituentother that hydrogen, for example R⁸ is trifluoromethyl; R, R³ and R⁵'sare chloro; M is —C(R³²R³³)—, where R³² and R³³ are methyl; q, r, s andu are 1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹ R²⁰, R²¹, R²² and R²³ are hydrogen, t,v and w are 0; x and y are 1; A, D and E are O, where D is attached tothe benzo-fused ring at the position designated as 1; and G is (CH₂)_(n)where n is 1;

[0126] Scheme 3, as depicted, offers an alternate route to the compoundsof the present invention different than that route set forth inScheme 1. The route of Scheme 3 is especially useful for adding asubstituent to the benzo-portion of the benzo-fused ring moiety.Accordingly, in a first series of steps, the known compound2,2-dimethyl-5-nitro-2,3-dihydrobenzo[2,3-b]furan-7-yl acetate wasreduced by hydrogenation under catalytic conditions affording thecorresponding 5-amino intermediate (D). Intermediate (D) was thentreated with tert-butyl nitrite, then halogenated with, for exampleelemental iodine, yielding the corresponding5-iodo-2,2-dimethyl-2,3-dihydrobenzo[2,3-b]furan-7-yl acetate (E).Intermediate (E) was in turn haloalkylated with2,2-difluoro-2-fluorosulfonyl acetate and copper iodide, providing thecorresponding2,2-dimethyl-5-(trifluoromethyl)-2,3-dihydrobenzo[2,3-b]furan-7-ylacetate (F), which was in turn de-protected by treating it with strongbase, affording the corresponding2,2-dimethyl-5-(trifluoromethyl)-2,3-dihydrobenzo[2,3-b]furan-7-ol (G).

[0127] In a second series of steps, 2,6-dichloro-4-phenylmethoxyphenol(known compound) was reacted under basic conditions with, for example4-chlorobutan-1-ol, as a means of attaching bridging group B, yieldingthe corresponding intermediate4-[2,6-dichloro-4-(phenylmethoxy)phenoxy]butan-1-ol (H). Intermediate(H) was then de-protected by cleavage of the phenylmethyl moiety usinghydrogenation under catalytic conditions affording the correspondingphenol intermediate (J), which was in turn reacted with, for example1,1,1,3-tetrachloropropane under basic conditions, affording thecorresponding butanol intermediate (K). Intermediate (K) was thenbrominated with, for example carbon tetrabromide and triphenylphosphine,providing the corresponding bromobutane intermediate (L). Intermediate(L) was in turn reacted with intermediate (G) under basic conditions,affording a compound of formula I where, for example R⁸ istrifluoromethyl (Compound 20). Example 3 set forth below, provides adetailed method to how Compound 20 shown in Scheme 3 was prepared.

[0128] Scheme 4 below illustrates a general procedure for synthesizingsubstituted arylalkene compounds of formula I where, for example, R¹,R², R⁴, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are hydrogen; R, R³ and R⁵'s are chloro;M is —C(R³²R³³)—, where R³² and R³³ are methyl; q, r s and t are 1,where R¹⁶, R¹⁷, R¹⁸, R¹⁹ R²⁰, and R²¹ are hydrogen and L is NHC(═O), u,v and w are 0; x and y are 1; A, D and E are O, where D is attached tothe benzo-fused ring at the position designated as 1; and G is (CH₂)_(n)where n is 1;

[0129] Scheme 4, as depicted provides a route to the compounds of thepresent invention where, inter alia, t is 1 and L is, for example amoiety such as NHC(═O). Accordingly, as a first step2,2-dimethyl-2,3-dihydrobenzo[2,3-b]furan-7-yl imidazolecarboxylate (M)was prepared by protecting the hydroxy group of2,2-dimethyl-2,3-dihydrobenzo[2,3-b]furan-7-ol by reacting it with1,1′-carbonyldiimidazole.

[0130] In another series of reactions,2,6-dichloro-4-phenylmethoxyphenol was first reacted with, for example(tert-butoxy)-N-(3-bromopropyl)carboxamide under basic conditions,providingN-{3-[2,6-dichloro-4-(phenylmethoxy)phenoxy]propyl}(tert-butoxy)carboxamide(N). Intermediate (N) was then de-protected by cleavage of thephenylmethyl moiety using hydrogenation under catalytic conditionsaffording the corresponding phenol intermediate (O), which was in turnreacted with, for example 1,1,1,3-tetrachloropropane under basicconditions, affording the corresponding carboxamide intermediate (P).Cleavage of the tert-butoxycarbonyl moiety from intermediate (P) underacidic conditions yielded, for example the amine hydrochloride saltintermediate (Q), which was then reacted with intermediate (M) underbasic conditions, affording a compound of formula I where, for example Lis NHC(═O) (Compound 53). Example 4 set forth below, provides a detailedmethod to how Compound 53 shown in Scheme 4 was prepared.

[0131] One skilled in the art will, of course, recognize that theformulation and mode of application of a toxicant may affect theactivity of the material in a given application. Thus, for agriculturaluse the present insecticidal compounds may be formulated as a granularof relatively large particle size (for example, 8/16 or 4/8 US Mesh), aswater-soluble or water-dispersible granules, as powdery dusts, aswettable powders, as emulsifiable concentrates, as aqueous emulsions, assolutions, or as any of other known types of agriculturally-usefulformulations, depending on the desired mode of application. It is to beunderstood that the amounts specified in this specification are intendedto be approximate only, as if the word “about” were placed in front ofthe amounts specified.

[0132] These insecticidal compositions may be applied either aswater-diluted sprays, or dusts, or granules to the areas in whichsuppression of insects is desired. These formulations may contain aslittle as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight ofactive ingredient.

[0133] Dusts are free flowing admixtures of the active ingredient withfinely divided solids such as talc, natural clays, kieselguhr, flourssuch as walnut shell and cottonseed flours, and other organic andinorganic solids which act as dispersants and carriers for the toxicant;these finely divided solids have an average particle size of less thanabout 50 microns. A typical dust formulation useful herein is onecontaining 1.0 part or less of the insecticidal compound and 99.0 partsof talc.

[0134] Wettable powders, also useful formulations for insecticides, arein the form of finely divided particles that disperse readily in wateror other dispersant. The wettable powder is ultimately applied to thelocus where insect control is needed either as a dry dust or as anemulsion in water or other liquid. Typical carriers for wettable powdersinclude Fuller's earth, kaolin clays, silicas, and other highlyabsorbent, readily wet inorganic diluents. Wettable powders normally areprepared to contain about 5-80% of active ingredient, depending on theabsorbency of the carrier, and usually also contain a small amount of awetting, dispersing or emulsifying agent to facilitate dispersion. Forexample, a useful wettable powder formulation contains 80.0 parts of theinsecticidal compound, 17.9 parts of Palmetto clay, and 1.0 part ofsodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester aswetting agents. Additional wetting agent and/or oil will frequently beadded to a tank mix for to facilitate dispersion on the foliage of theplant.

[0135] Other useful formulations for insecticidal applications areemulsifiable concentrates (ECs) which are homogeneous liquidcompositions dispersible in water or other dispersant, and may consistentirely of the insecticidal compound and a liquid or solid emulsifyingagent, or may also contain a liquid carrier, such as xylene, heavyaromatic naphthas, isphorone, or other non-volatile organic solvents.For insecticidal application these concentrates are dispersed in wateror other liquid carrier and normally applied as a spray to the area tobe treated. The percentage by weight of the essential active ingredientmay vary according to the manner in which the composition is to beapplied, but in general comprises 0.5 to 95% of active ingredient byweight of the insecticidal composition.

[0136] Flowable formulations are similar to ECs, except that the activeingredient is suspended in a liquid carrier, generally water. Flowables,like ECs, may include a small amount of a surfactant, and will typicallycontain active ingredients in the range of 0.5 to 95%, frequently from10 to 50%, by weight of the composition. For application, flowables maybe diluted in water or other liquid vehicle, and are normally applied asa spray to the area to be treated.

[0137] Typical wetting, dispersing or emulsifying agents used inagricultural formulations include, but are not limited to, the alkyl andalkylaryl sulfonates and sulfates and their sodium salts; alkylarylpolyether alcohols; sulfated higher alcohols; polyethylene oxides;sulfonated animal and vegetable oils; sulfonated petroleum oils; fattyacid esters of polyhydric alcohols and the ethylene oxide additionproducts of such esters; and the addition product of long-chainmercaptans and ethylene oxide. Many other types of useful surface-activeagents are available in commerce. Surface-active agents, when used,normally comprise 1 to 15% by weight of the composition.

[0138] Other useful formulations include suspensions of the activeingredient in a relatively non-volatile solvent such as water, corn oil,kerosene, propylene glycol, or other suitable solvents.

[0139] Still other useful formulations for insecticidal applicationsinclude simple solutions of the active ingredient in a solvent in whichit is completely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene, or other organic solvents. Granularformulations, wherein the toxicant is carried on relative coarseparticles, are of particular utility for aerial distribution or forpenetration of cover crop canopy. Pressurized sprays, typically aerosolswherein the active ingredient is dispersed in finely divided form as aresult of vaporization of a low-boiling dispersant solvent carrier mayalso be used. Water-soluble or water-dispersible granules are freeflowing, non-dusty, and readily water-soluble or water-miscible. In useby the farmer on the field, the granular formulations, emulsifiableconcentrates, flowable concentrates, aqueous emulsions, solutions, etc.,may be diluted with water to give a concentration of active ingredientin the range of say 0.1% or 0.2% to 1.5% or 2%.

[0140] The active insecticidal compounds of this invention may beformulated and/or applied with one or more second compounds. Suchcombinations may provide certain advantages, such as, withoutlimitation, exhibiting synergistic effects for greater control of insectpests, reducing rates of application of insecticide thereby minimizingany impact to the environment and to worker safety, controlling abroader spectrum of insect pests, safening of crop plants tophytotoxicity, and improving tolerance by non-pest species, such asmammals and fish.

[0141] Second compounds include, without limitation, other pesticides,plant growth regulators, fertilizers, soil conditioners, or otheragricultural chemicals. In applying an active compound of thisinvention, whether formulated alone or with other agriculturalchemicals, an effective amount and concentration of the active compoundis of course employed; the amount may vary in the range of, e.g. about0.001 to about 3 kg/ha, preferably about 0.03 to about 1 kg/ha. Forfield use, where there are losses of insecticide, higher applicationrates (e.g., four times the rates mentioned above) may be employed.

[0142] When the active insecticidal compounds of the present inventionare used in combination with one or more of second compounds, e.g., withother pesticides such as herbicides, the herbicides include, withoutlimitation, for example: N-(phosphonomethyl)glycine (“glyphosate”);aryloxyalkanoic acids such as (2,4-dichlorophenoxy)acetic acid(“2,4-D”), (4-chloro-2-methylphenoxy)acetic acid (“MCPA”),(+/−)-2-(4chloro-2-methylphenoxy)propanoic acid (“MCPP”); ureas such asN,N-dimethyl-N′-[4-(1-methylethyl)phenyl]urea (“isoproturon”);imidazolinones such as2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-pyridinecarboxylicacid (“imazapyr”), a reaction product comprising(+/−)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-4-methylbenzoicacid and(+/−)2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5-methylbenzoicacid (“imazamethabenz”),(+/−)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5-ethyl-3-pyridinecarboxylicacid (“imazethapyr”), and(+/−)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-quinolinecarboxylicacid (“imazaquin”); diphenyl ethers such as5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid(“acifluorfen”), methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate(“bifenox”), and5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenzamide(“fomasafen”); hydroxybenzonitriles such as4-hydroxy-3,5-diiodobenzonitrile (“ioxynil”) and3,5-dibromo-4-hydroxybenzonitrile (“bromoxynil”); sulfonylureas such as2-[[[[(4chloro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoicacid (“chlorimuron”),2-chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide(achlorsulfuron”),2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sufonyl]methyl]benzoicacid (“bensulfuron”),2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-1-methyl-1H-pyrazol-4-carboxylicacid (“pyrazosulfuron”),3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylicacid (“thifensulfuron”), and2-(2-chloroethoxy)-N[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide(“triasulfuron”); 2-(4-aryloxy-phenoxy)alkanoic acids such as(+/−)-2[4-[(6-chloro-2-benzoxazolyl)oxy]phenoxy]-propanoic acid(fenoxaprop”),(+/−)-2-[4[[5-(trifluoromethyl)-2-pyridinyl]oxy]-phenoxy]propanoic acid(“fluazifop”), (+/−)-2-[4-(6chloro-2-quinoxalinyl)oxy]-phenoxy]propanoicacid (“quizalofop”), and (+/−)-2-[(2,4-dichlorophenoxy)phenoxy]propanoicacid (“diclofop”); benzothiadiazinones such as3-(1-methylethyl)-1H-1,2,3-benzothiadiazin-4(3H)-one-2,2-dioxide(“bentazone”); 2-chloroacetanilides such asN-(butoxymethyl)-2-chloro-N-(2,6-diethylphenyl)acetamide (“butachlor”),2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide(“metolachlor”),2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide(“acetochlor”), and(RS)-2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide(“dimethenamide”); arenecarboxylic acids such as3,6-dichloro-2-methoxybenzoic acid (“dicamba”); pyridyloxyacetic acidssuch as [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]acetic acid(“fluroxypyr”), and other herbicides.

[0143] When the active insecticidal compounds of the present inventionare used in combination with one or more of second compounds, e.g., withother pesticides such as other insecticides, the other insecticidesinclude, for example: organophosphate insecticides, such aschlorpyrifos, diazinon, dimethoate, malathion, parathion-methyl, andterbufos; pyrethroid insecticides, such as fenvalerate, deltamethrin,fenpropathrin, cyfluthrin, flucythrinate, alpha-cypermethrin,bifenthrin, cypermethrin, resolved cyhalothrin, etofenprox,esfenvalerate, tralomehtrin, tefluthrin, cycloprothrin, betacyfluthrin,and acrinathrin; carbamate insecticides, such as aldecarb, carbaryl,carbofuran, and methomyl; organochlorine insecticides, such asendosulfan, endrin, heptachlor, and lindane; benzoylurea insecticides,such as diflubenuron, triflumuron, teflubenzuron, chlorfluazuron,flucycloxuron, hexaflumuron, flufenoxuron, and lufenuron; and otherinsecticides, such as amitraz, clofentezine, fenpyroximate, hexythiazox,spinosad, and imidacloprid.

[0144] When the active insecticidal compounds of the present inventionare used in combination with one or more of second compounds, e.g., withother pesticides such as fungicides, the fungicides include, forexample: benzimidazole fungicides, such as benomyl, carbendazim,thiabendazole, and thiophanate-methyl; 1,2,4-triazole fungicides, suchas epoxyconazole, cyproconazole, flusilazole, flutriafol, propiconazole,tebuconazole, triadimefon, and triadimenol; substituted anilidefungicides, such as metalaxyl, oxadixyl, procymidone, and vinclozolin;organophosphorus fungicides, such as fosetyl, iprobenfos, pyrazophos,edifenphos, and tolclofos-methyl; morpholine fungicides, such asfenpropimorph, tridemorph, and dodemorph; other systemic fungicides,such as fenarimol, imazalil, prochloraz, tricyclazole, and triforine;dithiocarbamate fungicides, such as mancozeb, maneb, propineb, zineb,and ziram; non-systemic fungicides, such as chlorothalonil,dichlofluanid, dithianon, and iprodione, captan, dinocap, dodine,fluazinam, gluazatine, PCNB, pencycuron, quintozene, tricylamide, andvalidamycin; inorganic fungicides, such as copper and sulphur products,and other fungicides.

[0145] When the active insecticidal compounds of the present inventionare used in combination with one or more of second compounds, e.g., withother pesticides such as nematicides, the nematicides include, forexample: carbofuran, carbosulfan, turbufos, aldicarb, ethoprop,fenamphos, oxamyl, isazofos, cadusafos, and other nematicides.

[0146] When the active insecticidal compounds of the present inventionare used in combination with one or more of second compounds, e.g., withother materials such as plant growth regulators, the plant growthregulators include, for example: maleic hydrazide, chlormequat,ethephon, gibberellin, mepiquat, thidiazon, inabenfide, triaphenthenol,paclobutrazol, unaconazol, DCPA, prohexadione, trinexapac-ethyl, andother plant growth regulators.

[0147] Soil conditioners are materials which, when added to the soil,promote a variety of benefits for the efficacious growth of plants. Soilconditioners are used to reduce soil compaction, promote and increaseeffectiveness of drainage, improve soil permeability, promote optimumplant nutrient content in the soil, and promote better pesticide andfertilizer incorporation. When the active insecticidal compounds of thepresent invention are used in combination with one or more of secondcompounds, e.g., with other materials such as soil conditioners, thesoil conditioners include organic matter, such as humus, which promotesretention of cation plant nutrients in the soil; mixtures of cationnutrients, such as calcium, magnesium, potash, sodium, and hydrogencomplexes; or microorganism compositions which promote conditions in thesoil favorable to plant growth. Such microorganism compositions include,for example, bacillus, pseudomonas, azotobacter, azospirillum,rhizobium, and soil-borne cyanobacteria.

[0148] Fertilizers are plant food supplements, which commonly containnitrogen, phosphorus, and potassium. When the active insecticidalcompounds of the present invention are used in combination with one ormore of second compounds, e.g., with other materials such asfertilizers, the fertilizers include nitrogen fertilizers, such asammonium sulfate, ammonium nitrate, and bone meal; phosphatefertilizers, such as superphosphate, triple superphosphate, ammoniumsulfate, and diammonium sulfate; and potassium fertilizers, such asmuriate of potash, potassium sulfate, and potassium nitrate, and otherfertilizers.

[0149] The following examples further illustrate the present invention,but, of course, should not be construed as in any way limiting itsscope. The examples are organized to present protocols for the synthesisof the compounds of formula I of the present invention, set forth a listof such synthesized species, and set forth certain biological dataindicating the efficacy of such compounds.

EXAMPLE 1 This example illustrates the preparation of5-(3,3-Dichloroprop-2-enyloxy)-2-[4-(2,2-dimethyl(2,3-dihydrobenzo[2,3-b]furan-7-yloxy))butoxy]-1,3-dichlorobenzene(Compound 12 in table below)

[0150] Step A Synthesis of1,3-Dichloro-2-(4-chlorobutoxy)-5-(phenylmethoxy)benzene as anIntermediate

[0151] A stirred solution of 7.5 grams (0.028 mole) of2,6-dichloro-4-phenylmethoxyphenol (known compound) and 3 mL (0.030mole) of 1-bromo-4-chlorobutane in 225 mL of DMF was cooled in an icebath, and 5.8 grams (0.042 mole) of potassium carbonate was added. Uponcompletion of addition, the reaction mixture was allowed to warm toambient temperature as it stirred for about 18 hours. The reactionmixture was then poured into 1000 mL of an aqueous solution saturatedwith sodium chloride. The mixture was extracted with four 150 mLportions of diethyl ether, and the combined extracts were washed with 50mL of water. The organic layer was dried with sodium sulfate, filtered,and concentrated under reduced pressure to a residue. The residue waspurified with column chromatography on silica gel using 1:3 methylenechloride:hexane as an eluant. The appropriate fractions were combinedand concentrated under reduced pressure, yielding 6.7 grams of thesubject compound. The NMR spectrum was consistent with the proposedstructure.

[0152] Step B Synthesis of2-[4-(2,2-dimethyl(2,3-dihydrobenzo[2,3-b]furan-7-yloxy))butoxy]-1,3-dichloro-5-(phenylmethoxy)benzeneas an Intermediate

[0153] A stirred solution of 1.0 gram (0.0028 mole) of1,3-dichloro-2-(4-chlorobutoxy)-5-(phenylmethoxy)benzene, 0.6 gram(0.0034 mole) of 2,2-dimethyl-2,3-dihydrobenzo[b]furan-7-ol (knowncompound), and 0.6 gram (0.0043 mole) of potassium carbonate in 25 mL ofDMF was heated at 80° C. for about 18 hours. After this time, thereaction mixture was cooled and 50 mL of water was added. The mixturewas then extracted with three 25 mL portions of diethyl ether. Thecombined extracts were washed with 25 mL of an aqueous solutionsaturated with sodium chloride. The organic layer was dried with sodiumsulfate, filtered, and concentrated under reduced pressure to a residue.The residue was purified with column chromatography on silica gel usingmixtures of 1:3 methylene chloride:hexane and 1:1 methylenechloride:hexane as eluants. The appropriate fractions were combined andconcentrated under reduced pressure, yielding 0.87 gram of the subjectcompound. The NMR spectrum was consistent with the proposed structure.

[0154] Step C Synthesis of4-[4-(2,2-dimethyl(2,3-dihydrobenzo[2,3-b]furan-7-yloxy))butoxy]-3,5-dichlorophenolas an Intermediate

[0155] A mixture of 0.67 gram (0.0014 mole) of,2-[4-(2,2-dimethyl(2,3-dihydrobenzo[2,3-b]furan-7-yloxy))butoxy]-1,3-dichloro-5-(phenylmethoxy)benzeneand 0.01 gram (catalyst) of 10% palladium on carbon in 75 mL of methanolwas subjected to hydrogenation conditions using a Parr Hydrogenator,yielding 0.55 gram of the subject compound. The NMR spectrum wasconsistent with the proposed structure.

[0156] Step D Synthesis of Compound 12

[0157] A stirred solution of 0.44 gram (0.0011 mole) of4-[4-(2,2-dimethyl(2,3-dihydrobenzo[2,3-b]furan-7-yloxy))butoxy]-3,5-dichlorophenol,0.3 gram (0.0015 mole) of 1,1,1,3-tetrachloropropane, and 0.3 gram(0.0022 mole) of potassium carbonate in 25 mL of DMF was heated at 80°C. for about 18 hours. After this time, the reaction mixture was cooled,and then it was poured into 50 mL of water. The mixture was saturatedwith solid sodium chloride and extracted with three 25 mL portions ofdiethyl ether. The combined extracts were washed with 25 mL of water anddried with sodium sulfate. The mixture was filtered, and the filtratewas concentrated under reduced pressure to a residue. The residue waspurified with column chromatography on silica gel using 1:1 methylenechloride:hexane as an eluant. The appropriate fractions were combinedand concentrated under reduced pressure, yielding 0.39 gram of compound15. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 2 This example illustrates the preparation of7-{4-[4-(3,3-dichloroprop-2-enyloxy)-2,6-dichlorophenoxy]butoxy}2,2-dimethyl-2-hydrobenzo[b]furan-3-one(Compound 36 in table below)

[0158] A mixture of 0.20 gram (0.0004 mole) of Compound 12 (Prepared inExample 1), 0.26 gram (0.0010 mole) of potassium persulfate, and 0.10gram (0.0004 mole) of copper sulfate pentasulfate in 15 mL ofacetonitrile and 15 mL of water was stirred at 80° C. during a one hourperiod. After this time the reaction mixture was allowed to cool toambient temperature, then it was extracted with two 15 mL portions ofdiethyl ether. The combined extracts were washed with one 15 mL portionof water, dried with sodium sulfate and filtered. The filtrate wasconcentrated under reduced pressure to a residual semi-solid. Thesemi-solid was purified with column chromatography on silica gel usingmethylene chloride as an eluant. The appropriate fractions were combinedand concentrated under reduced pressure, yielding 0.03 gram of compound36. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 3 This example illustrates the preparation of5-(3,3-dichloroprop-2-enyloxy)-2-{4-[2,2-dimethyl-5-(trifluoromethyl)(2,3-dihydrobenzo[2,3-b]furan-7-yloxy)]-butoxy}1,3-dichlorobenzene(Compound 20 in table below)

[0159] Step A Synthesis of5-amino-2,2-dimethyl-2,3-dihydrobenzo[2,3-b]furan-7-yl acetate as anIntermediate

[0160] A mixture of 3.5 grams (0.014 mole) of2,2-dimethyl-5-nitro-2,3-dihydrobenzo[2,3-b]furan-7-yl acetate (knowncompound) and a catalytic amount of 10% palladium on carbon in 125 mL ofethanol was subjected to hydrogenation conditions using a ParrHydrogenator. Upon completion of the uptake of the theoretical amount ofhydrogen, the reaction mixture was filtered and concentrated underreduced pressure to a residue. The residue was purified with columnchromatography on silica gel using methylene chloride, followed by 5%methanol in methylene chloride as eluants. The appropriate fractionswere combined and concentrated under reduced pressure, yielding 2.7grams of the subject compound. The NMR spectrum was consistent with theproposed structure.

[0161] Step B Synthesis of5-iodo-2,2-dimethyl-2,3-dihydrobenzo[2,3-b]furan-7-yl acetate as anIntermediate

[0162] A stirred solution of 1.0 gram (0.0045 mole) of5-amino-2,2-dimethyl-2,3-dihydrobenzo[2,3-b]furan-7-yl acetate in 40 mLof acetonitrile was cooled in an ice-bath and 0.55 mL (0.0045 mole) oftert-butyl nitrite was added. Upon completion of addition, the reactionmixture was stirred for an additional 15 minutes with continued cooling.After this time 1.2 grams (0.0045 mole) of iodine was added in twoportions during a five-minute period. Upon completion of addition, thereaction mixture was stirred for an additional one hour with continuedcooling, allowed to warm to ambient temperature where it stirred forthree hours, and then it was warmed to reflux where it stirred for 30minutes. After this time the reaction mixture was cooled and poured into50 mL of aqueous 10% hydrochloric acid and the mixture was extractedwith two 25 mL portions of methylene chloride. The combined extractswere washed with one 25 mL portion of an aqueous solution saturated withsodium chloride, dried with sodium sulfate, and filtered. The filtratewas concentrated under reduced pressure to a residue. The residue waspurified with column chromatography on silica gel using methylenechloride as an eluant. The appropriate fractions were combined andconcentrated under reduced pressure, yielding 0.78 gram of the subjectcompound. The NMR spectrum was consistent with the proposed structure.The reaction was repeated to obtain additional intermediate.

[0163] Step C Synthesis of2,2-dimethyl-5-(trifluoromethyl)-2,3-dihydro[2,3-b]furan-7-yl acetate asan Intermediate

[0164] A stirred mixture of 1.2 grams (0.0037 mole) of5-iodo-2,2-dimethyl-2,3-dihydrobenzo[2,3-b]furan-7-yl acetate, 1.5 grams(0.0074 mole) of methyl 2,2-difluoro-2-fluorosulfonyl acetate and 0.2gram (0.001 mole) of copper iodide in 50 mL of DMF was heated at 80° C.during a six-hour period. A GC analysis of the reaction mixture afterthis time indicated that the reaction was about 70% complete. Anadditional 0.5 gram of methyl 2,2-difluoro-2-fluorosulfonyl acetate and0.1 gram of copper iodide were added to the reaction mixture, and theheating at 80° C. was continued for an additional 18 hour period. Thereaction mixture was allowed to cool to ambient temperature and then itwas poured into 75 mL of water and extracted with three 25 mL portionsof diethyl ether. The combined extracts were washed with two 25 mLportions of water, dried with sodium sulfate, and filtered. The filtratewas concentrated under reduced pressure to a residue. The residue waspurified with column chromatography on silica gel using a mixture of 1:1methylene chloride and hexane as an eluant. The appropriate fractionswere combined and concentrated under reduced pressure, yielding 0.60gram of the subject compound. The NMR spectrum was consistent with theproposed structure.

[0165] Step D Synthesis of2,2-dimethyl-5-(trifluoromethyl)-2,3-dihydro[2,3-b]furan-7-ol as anIntermediate

[0166] A solution of 0.6 gram (0.0022 mole) of2,2-dimethyl-5-(trifluoromethyl)-2,3-dihydro[2,3-b]furan-7-yl acetate in5 mL of methanol was stirred and a solution of 0.9 gram (0.0220 mole) ofsodium hydroxide in 15 mL of water was added. Upon completion ofaddition the reaction mixture was warmed to 40° C. where it stirred fortwo hours. After this time the reaction mixture was allowed to cool toambient temperature as it stirred during an 18 hour period. The reactionmixture was then acidified to a pH of 6 using concentrated hydrochloricacid and then it was extracted with three 25 mL portions of diethylether. The combined extracts were washed with one 25 mL portion ofwater, dried with sodium sulfate, and filtered. The filtrated wasconcentrated under reduced pressure, yielding 0.4 gram of the subjectcompound. The NMR spectrum was consistent with the proposed structure.

[0167] Step E Synthesis of4-[2,6-dichloro-4-(phenylmethoxy)phenoxy]butan-1-ol as an Intermediate

[0168] A solution of 33.9 grams (0.126 mole) of2,6-dichloro-4-phenylmethoxyphenol (known compound), 16.4 grams (0.151mole) of 4-chlorobutan-1-ol and 20.9 grams (0.151 mole) of potassiumcarbonate in 300 mL of DMF was warmed to 80° C. where it stirred duringan 18 hour period. After this time the reaction mixture was concentratedunder reduced pressure to a residue. Water was added to the residue andthe mixture was extracted with ethyl acetate. The extract was washedwith water and then with an aqueous solution saturated with sodiumchloride. The organic layer was dried with magnesium sulfate andfiltered, and the filtrate was concentrated under reduced pressure to aresidue. The residue was purified with column chromatography on silicagel using a mixture of 1:1 ethyl acetate and hexane as an eluant. Theappropriate fractions were combined and concentrated under reducedpressure, yielding 12.2 grams of the subject compound. The NMR spectrumwas consistent with the proposed structure.

[0169] Step F Synthesis of 3,5-dichloro-4-(4-hydroxybutoxy)phenol as anIntermediate

[0170] This compound was prepared in a manner analogous to that of StepA of this example, using 12.2 grams (0.036 mole) of4-[2,6-dichloro-4-(phenylmethoxy)phenoxy]butan-1-ol and 0.5 gram(catalyst) of 10% palladium on carbon and a theoretical amount ofhydrogen gas in a Parr Hydrogenator. The yield of the subject compoundwas 9.3 grams. The NMR spectrum was consistent with the proposedstructure.

[0171] Step G Synthesis of4-[4-(3,3-dichloroprop-2-enyloxy)-2,6-dichlorophenoxy]butan-1-ol as anIntermediate

[0172] This compound was prepared in a manner analogous to that of StepD of Example 1, using 9.3 grams (0.036 mole) of3,5-dichloro-4-(4-hydroxybutoxy)phenol, 7.7 grams (0.042 mole) of1,1,1,3-tetrachloropropane and 11.7 grams (0.080 mole) of potassiumcarbonate in 300 mL of DMF. The crude product was purified with columnchromatography on silica gel using mixtures of 1:4 and 1:1 ethyl acetateand hexane as eluants. The appropriate fractions were combined andconcentrated under reduced pressure, yielding 8.0 grams of the subjectcompound. The NMR spectrum was consistent with the proposed structure.

[0173] Step H Synthesis of1-[4-(3,3-dichloroprop-2-enyloxy)-2,6-dichlorophenoxy]-4-bromobutane asan Intermediate

[0174] A stirred solution of 7.3 grams (0.020 mole) of4-[4-(3,3-dichloroprop-2-enyloxy)-2,6-dichlorophenoxy]butan-1-ol in 400mL of methylene chloride was cooled in an ice bath and, in turn, 5.5grams (0.021 mole) of triphenylphosphine and 6.9 grams (0.021 mole) ofcarbon tetrabromide were added. Upon completion of addition the reactionmixture was stirred with continued cooling for one hour, then it wasallowed to warm to ambient temperature where it stirred during an18-hour period. After this time the reaction mixture was concentratedunder reduced pressure to a residue. The residue was purified withcolumn chromatography on silica gel using hexane and a mixture of 1:1methylene chloride and heptane as an eluant. The appropriate fractionswere combined and concentrated under reduced pressure, yielding 12.2grams of the subject compound. The NMR spectrum was consistent with theproposed structure.

[0175] Step I Synthesis of Compound 20

[0176] Under a nitrogen atmosphere, a solution of 0.18 gram (0.0004)mole of1-[4-(3,3-dichloroprop-2-enyloxy)-2,6-dichlorophenoxy]-4-bromobutane,0.10 gram (0.0004 mole) of2,2-dimethyl—5-(trifluoromethyl)-2,3-dihydro[2,3-b]furan-7-ol (preparedin Step D of this example) and 0.09 gram (0.0007 mole) of potassiumcarbonate in 15 mL of DMF was stirred at ambient temperature during an18-hour period. After this time the reaction mixture was stirred with 25mL of water and was saturated with solid sodium chloride. The mixturewas then extracted with two 25 mL portions of diethyl ether; and thecombined extracts were washed with one 25 mL portion of water, driedwith sodium sulfate, filtered and concentrated under reduced pressure toa residue. The residue was purified with column chromatography on silicagel using hexane and a mixture of 1:1 methylene chloride and hexane aseluants. The appropriate fractions were combined and concentrated underreduced pressure, yielding 0.19 gram of compound 20. The NMR spectrumwas consistent with the proposed structure.

EXAMPLE 4 This example illustrates the preparation ofN-{3-[4-(3,3-dichloroprop-2-enyloxy)-2,6-dichlorophenoxy]propyl}(2,2-dimethyl(2,3-dihydrobenzo[2,3-b]furan-7-yloxy))-carboxamide(Compound 53 in table below)

[0177] Step A Synthesis of2,2-dimethyl-2,3-dihydrobenzo[2,3-b]benzofuran-7-yl imidazolecarboxylateas an Intermediate

[0178] A solution of 1.64 grams (0.010 mole) of2,2-dimethyl-2,3-dihydrobenzo[b]furan-7-ol (known compound) in 30 mL ofmethylene chloride was stirred, and 1.62 grams (0.010 mole) of1,1′-carbonyldiimidazole was added in one portion. Upon completion ofaddition the reaction mixture was stirred at ambient temperature for 20minutes. After this time the reaction mixture was concentrated underreduced pressure to a residue. The residue was dissolved in a mixture of1:1 methylene chloride and hexanes and purified by column chromatographyon silica gel using a mixture of 7:4 hexane and ethyl acetate as aneluant. The appropriate fractions were combined and concentrated underreduced pressure, yielding 1.96 grams of the subject compound. The NMRspectrum was consistent with the proposed structure.

[0179] Step B Synthesis ofN-{3-[2,6-dichloro-4-(phenylmethoxy)phenoxy]propyl}(tert.-butoxy)carboxamideas an Intermediate

[0180] A solution of 2.69 grams (0.010 mole) of2,6-dichloro-4-phenylmethoxyphenol (known compound), 2.38 grams (0.010mole) of (tert-butoxy)-N-(3-bromopropyl)carboxamide (commerciallyavailable) and 1.52 grams (0.011 mole) of potassium carbonate in 40 mLof DMF was stirred at ambient temperature during a four-day period.After this time the reaction mixture was shaken in diethyl ether andwater, and the separated organic layer was washed with one portion ofwater and with one portion of an aqueous solution saturated with sodiumchloride. The organic layer was dried with sodium sulfate and filtered.The filtrate was concentrated under reduced pressure, yielding 4.15grams of the subject compound.

[0181] Step C Synthesis ofN-[3-(2,6-dichloro-4-hydroxyphenoxy)propyl](tert-butoxy)carboxamide asan Intermediate

[0182] This compound was prepared in a manner analogous to that of StepA of Example 3, using 4.1 grams (0.0096 mole) ofN-{3-[2,6-dichloro-4-(phenylmethoxy)phenoxy]propyl}(tert.-butoxy)carboxamide,a catalytic amount of 10% palladium on carbon and a theoretical amountof hydrogen gas in 60 mL of 1:1 ethanol and ethyl acetate in a ParrHydrogenator. The yield of the subject compound was 3.5 grams.

[0183] Step D Synthesis ofN-{3-[4-(3,3-dichloroprop-2-enyloxy)-2,6-dichlorophenoxy]propyl}(tert-butoxy)carboxamideas an Intermediate

[0184] This compound was prepared in a manner analogous to that of StepD of Example 1, using 3.5 grams (0.0104 mole) ofN-[3-(2,6-dichloro-4-hydroxyphenoxy)propyl](tert-butoxy)carboxamide, 2.3grams (0.0125 mole) of 1,1,1,3-tetrachloropropane and 3.4 grams (0.0250mole) of potassium carbonate in DMF. The crude product was purified withcolumn chromatography on silica gel using a mixture of 1:3 hexane andmethylene chloride as an eluant. The appropriate fractions were combinedand concentrated under reduced pressure, yielding 2.6 grams of thesubject compound. The NMR spectrum was consistent with the proposedstructure.

[0185] Step E Synthesis of3-[4-(3,3-dichloroprop-2-enyloxy)-2,6-dichlorophenoxy]propylaminehydrochloride as an Intermediate

[0186] A stirred solution of 2.6 grams (0.0058 mole) ofN-{3-[4-(3,3-dichloroprop-2-enyloxy)-2,6-dichlorophenoxy]propyl}(tert-butoxy)carboxamidein 10 mL of anhydrous diethyl ether was cooled to 0° C. and a 2Nsolution of hydrogen chloride in diethyl ether was added via a syringe.Upon completion of addition the reaction mixture was allowed to warm toambient temperature where it stirred during an 18-hour period. Aresultant solid precipitate was collected by filtration, yielding whendried, 1.25 grams of the subject compound. The filtrate was taken up inhexanes and allowed to stand during an 18-hour period, during which timea second crop of the subject compound precipitated from the filtrate.The precipitate was collected by filtration and dried, yielding anadditional 0.83 gram of the subject compound.

[0187] Step F Synthesis of Compound 53

[0188] A solution of 82 milligrams (0.318 mmole) of2,2-dimethyl-2,3-dihydrobenzo[2,3-b]benzofuran-7-yl imidazolecarboxylate(prepared in Step A of this example), 100 milligrams (0.262 mmole) of3-[4-(3,3-dichloroprop-2-enyloxy)-2,6-dichlorophenoxy]propylaminehydrochloride and 73 microliters (0.524 mmole) of triethylamine in fivemL of methylene chloride was stirred at ambient temperature during an18-hour period. After this time TLC analysis of the reaction mixtureindicated that no reaction had taken place. The reaction mixture wasconcentrated under reduced pressure to remove the methylene chloride,and five mL of acetonitrile was added. The reaction mixture was thenheated at reflux during an 18-hour period after which time TLC analysisindicated that the reaction had taken place, albeit incomplete. Thereaction mixture was then concentrated under reduced pressure to aresidue. The residue was dissolved in a mixture of 1:1 dichloromehaneand hexanes and purified by column chromatography on silica gel using amixture of 4:1 hexane and ethyl acetate as an eluant. The appropriatefractions were combined and concentrated under reduced pressure,yielding 45 milligrams of compound 53. The NMR spectrum was consistentwith the proposed structure.

[0189] It is well known to one of ordinary skill in the art thatcompounds like the compounds of formula I of the present invention cancontain optically active and racemic forms. It is also well known in theart that compounds like the compounds of formula I may containstereoisomeric forms, tautomeric forms and/or exhibit polymorphism. Itis to be understood that the present invention encompasses any racemic,optically active, polymorphic, tautomeric, or stereoisomeric form, ormixtures thereof. It should be noted that it is well known in the arthow to prepare optically active forms, for example by resolution of aracemic mixture, or by synthesis from optically active intermediates.

[0190] The following table sets forth examples of compounds of formulaI: TABLE 1 Insecticidal (dihalopropenyl) phenylalkyl substituteddihydrobenzofuran and dihydrobenzopyran derivatives

where B is a bridging group of the formula:—(CR¹⁶R¹⁷)_(q)—(CR¹⁸R¹⁹)_(r)—(CR²⁰R²¹)_(s)—L_(t)—(CR²²R²³)_(u)—(CR²⁴R²⁵)_(v)—(CR²⁶R²⁷)_(w)—. where R¹, R², R⁴, R¹⁰ and R¹¹ arehydrogen; R, R³ and R⁵'s are chloro; M is —C(R³²R³³)—, where R³² and R³³are methyl; q and r are 1, where R¹⁶, R¹⁷, R¹⁸ and R¹⁹ are hydrogen; s,t, u, v and w are 0; x and y are 1; A, D and E are O, and G is (CH₂)_(n)where n is 1; providing compounds of formula IA as set forth below:

Cmpd. Point of attachment of No. D to Benzo-fused ring R⁶ R⁷ R⁸ R⁹ 1 1 —H Cl H where R¹, R², R⁴, R¹⁰ and R¹¹ are hydrogen; R, R³ and R⁵'s arechloro; M is —C(R³² R³³ )—, where R³² and R³³ are methyl; q, r and s are1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²² and R²³ are hydrogen, andunless otherwise noted R²⁰ is hydrogen; t, u, v and w are 0; x and y are1; A, D and E are O, and G is (CH₂)_(n) where n is 1; providingcompounds of formula IB as set forth below:

Cmpd. Point of attachment of No. D to Benzo-fused ring R⁶ R⁷ R⁸ R⁹ 2 1 —H H H 3 1 — H H Cl 4 1 — H Cl H  5* 1 — H Cl H 6 1 — H Br H 7 1 — H NO₂H 9 1 — H NHCO₂C₂H₅ H where R², R⁴, R¹⁰ and R¹¹ are hydrogen; R and R⁵'sare chloro; M is —C(R³²R³³)—, where R³² and R³³ are methyl; q, r, s andu are 1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹ R²⁰, R²¹, R²² and R²³ are hydrogen, t,v and w are O; x and y are 1; A, D and E are O, and G is (CH₂)_(n) wheren is 1; providing compounds of formula IC as set forth below:

Point of attachment of D Cmpd. to Benzo-fused No. R¹ R³ ring R⁶ R⁷ R⁸ R⁹10 H H 1 — H H H 11 H Cl 4 H H H — 12 H Cl 1 — H H H 13 Cl Cl 1 — H H H14 H Cl 4 Cl H H — 15 H Cl 1 — H H Cl 16 H Cl 1 — H Cl H 17 H Cl 1 — H HBr 18 H Cl 1 — H Br H 19 H Cl 1 — H I H 20 H Cl 1 — H CF₃ H 21 H Cl 1 —H C≡N H 22 H Cl 1 — H NO₂ H 23 H Cl 1 — NO₂ H CH₃ 24 H Cl 1 — H NH₂ H 25H Cl 1 — H NHC(═O)CH₃ H 26 H Cl 1 — H NHC(═O)Ph H 27 H Cl 1 — HNHCO₂C₂H₅ H 28 H Cl 1 — H Ph H where R¹, R², R⁴ and R¹¹ are hydrogen; R,R³ and R⁵'s are chloro; M is —C(R³²R³³)—, where R³² and R³³ are methyl;q, r, s and u are 1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹ R²⁰, R²¹, R²² and R²³ arehydrogen, t, v and w are O; x and y are 1; A, D and E are O, and G is(CH₂)_(n) where n is 1; providing compounds of formula ID as set forthbelow:

Cmpd. Point of attachment of D No. to Benzo-fused ring R⁶ R⁷ R⁸ R⁹ R¹⁰29 1 — H H H F 30 1 — H H H OH where R¹, R², R⁴, R¹⁰ and R¹¹ arehydrogen, R, R³ and R⁵'s are chloro; M is —C(R³²R³³)—, where R³² and R³³are methyl; q, r, s and u are 1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹ R²⁰, R²¹, R²²and R²³ are hydrogen, t, v and w are O; x and y are 1; A and E are O, Dis NR¹⁵ and G is (CH₂)_(n) where n is 1; providing compounds of formulaIE as set forth below:

Point of attachment Cmpd. of D to Benzo-fused No. ring R⁶ R⁷ R⁸ R⁹ R¹⁵31 1 — H H H CH₂CH═C(Cl)₂ 32 1 — H H H C(═O)CH₃ where R¹, R², and R⁴ arehydrogen; R, R³ and R⁵'s are chloro; M is —C(R³²R³³)—; q, r, s and u are1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²² and R²³ are hydrogen, t, vand w are 0; x and y are 1; A, D and E are O, and G is (CH₂)_(n) where nis 1; providing compounds of formula IF as set forth below:

Point of attachment Cmpd. of D to Benzo No. fused ring R⁶ R⁷ R⁸ R⁹ R¹⁰R¹¹ R³² R³³ 33 1 — H H H F F F F where R¹, R² and R⁴ are hydrogen; R, R³and R⁵'s are chloro; R¹⁰ and R¹¹ are taken together with —SCH₂CH₂S— toform a thioketal; M is —C(R³² R³³ )—, where R³² and R³³ are methyl; q,r, s and u are 1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²² and R²³ arehydrogen, t, v and w are 0; x and y are 1; A, D and E are O, and G is(CH₂)_(n) where n is 1; providing compounds of formula IG as set forthbelow:

Cmpd. Point of attachment of D to No. R¹ R³ Benzo-fused ring R⁶ R⁷ R⁸ R⁹34 H H 1 — H H H where R¹, R², and R⁴ are hydrogen; R, R³ and R⁵'s arechloro; R¹⁰ and R¹¹ are taken together with O to form a carbonyl group;M is —C(R³²R³³)—, where R³² and R³³ are methyl; q, r and s are 1, whereR¹⁶, R¹⁷, R¹⁸, R¹⁹ and R²¹ are hydrogen; t and w are 0; x and y are 1; uand v are 0 or 1 and when u and v are 1, R²², R²³, R²⁴ and R²⁵ arehydrogen; A, D and E are O, and G is (CH₂)_(n) where n is 1; and thebenzo-fused ring is attached at the 1-position, providing compounds offormula IH as set forth below:

Cmpd. No u v R⁷ R⁸ R⁹ 35 0 0 H H H 36 1 0 H H H 37 1 0 H H Cl 38 1 0 HCl H 39 1 0 Cl H Cl 40 1 1 Cl H Cl where R¹, R², R⁴, R¹⁰ and R¹¹ arehydrogen; R, R³ and R⁵'s are chloro; M is —C(R³²R³³)—, where R³² and R³³are methyl; q, r, s, u and v are 1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹ R²⁰, R²¹,R²², R²³, R²⁴ and R²⁵ and R²⁵ are hydrogen, t and w are 0; x and y are1; A, D and E are O, and G is (CH₂)_(n) where n is 1; providingcompounds of formula II as set forth below:

Cmpd. Point of attachment of D No. to Benzo-fused ring R⁶ R⁷ R⁸ R⁹ 41 1— H H H 42 1 — H Cl H 43 1 — H Br H 44 1 — H CF₃ H where R¹, R², R⁴, R¹⁰and R¹¹ are hydrogen; R, R³ and R⁵'s are choro; M is —C(R³²R³³)—, whereR³² and R³³ are methyl; q, r, s, u and v are 1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹R²⁰, R²¹, R²², R²³, R²⁴ and R²⁵ are hydrogen, t and w are 0; x and y are1; A and E are O, and G is (CH₂)_(n) where n is 1; and D is NR¹⁵providing compounds of formula IJ as set forth below:

Cmpd. Point of attachment of No. D to Benzo-fused ring R⁶ R⁷ R⁸ R⁹ R¹⁵45 1 — H H H H 46 1 — H H H CH₃ 47 1 — H H H CH₂C═CH₂ 48 1 — H H H CH₂Phwhere R¹, R², R⁴, R¹⁰ and R¹¹ are hydrogen; R, R³ and R⁵'s are chloro; Mis —C(R³² R³³ )—, where R³² and R³³ are methyl; q, r, u and v are 1,where R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²², R²³, R²⁴ and R²⁵ are hydrogen, t is 1; sand w are 0; x and y are 1; A, D, E and L are O, and G is (CH₂)_(n)where n is 1; providing compounds of formula IK as set forth below:

Cmpd. Point of attachment of D No. to Benzo-fused ring R⁶ R⁷ R⁸ R⁹ 49 1— H H H 50 1 — H Cl H where R¹, R², R⁴, R¹⁰ and R¹¹ are hydrogen; R, R³and R⁵'s are chloro; M is —C(R³²R³³)—, where R³² and R³³ are methyl; q,r, s, u, v and w are 1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹ R²⁰, R²¹, R²², R²³,R²⁴, R²⁵, R²⁶ and R²⁷ are hydrogen, t is 0; x and y are 1; A, D and Eare O, and G is (CH₂)_(n) where n is 1; providing compounds of formulaIL as set forth below:

Cmpd. Point of attachment of D No. to Benzo-fused ring R⁶ R⁷ R⁸ R⁹ 51 1— H H H where R¹, R², R⁴, R¹⁰ and R¹¹ are hydrogen; R, R³ and R⁵'s arechloro; M is —C(R³² R³³ )—, where R³² and R³³ are methyl; q, r s and tare 1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹ R²⁰, and R²¹ are hydrogen and L isOC(═O), u, v and w are 0; x and y are 1; A and E are O; D is NR¹⁵ whereR¹⁵ is hydrogen; and G is (CH₂)_(n) where n is 1; providing compounds offormula IM as set forth below:

Cmpd. Point of attachment of D No. to Benzo-fused ring R⁶ R⁷ R⁸ R⁹ 52 1— H H H where R¹, R², R⁴R¹⁰ and R¹¹ are hydrogen; R, R³ and R⁵'s arechloro; M is —C(R³²R³³)—, where R³²R³³ are methyl; q, r s and t are 1,where R¹⁶, R¹⁷, R¹⁸, R¹⁹ R²⁰, and R²¹ are hydrogen and L is NHC(═O), u,v and w are 0; x and y are 1; A, D and E are O, and G is (CH₂)_(n) wheren is 1; providing compounds of formula IN as set forth below:

Cmpd. Point of attachment of D No. to Benzo-fused ring R⁶ R⁷ R⁸ R⁹ 53 1— H H H where R¹, R², R⁴, R¹⁰, and R¹¹ are hydrogen; R, R³ and R⁵'s arechloro; M is —C(R³² R³³ )C(R³⁴R³⁵)—, where R³² and R³³ are hydrogen andR³⁴ and R³⁵ are methyl; q, r, s and u are 1, where R¹⁶, R¹⁷, R¹⁸, R¹⁹R²⁰, R²¹, R²² and R²³ are hydrogen, t, v and w are 0; x and y are 1; A,D and E are O, and G is (CH₂)_(n) where n is 1; providing compounds offormula IO as set forth below:

Cmpd. Point of attachment of D to No. Benzo-fused ring R⁶ R⁷ R⁸ R⁹ 54 1— H H Cl

[0191] TABLE 2 Insecticidal (dihalopropenyl) phenylalkyl substituteddihydrobenzofuran and dihydrobenzopyran derivatives Characterizing DataCmpd. Emperical Physical Cmpd. Emperical Physical No. Formulae State No.Formulae State 1 C₂₁H₁₉Cl₅O₄ Solid 2 C₂₂H₂₂Cl₄O₄ Liquid 3 C₂₂H₂₁Cl₅O₄Liquid 4 C₂₂H₂₁Cl₅O₄ Solid, 86-90° C. 5 C₂₃H₂₃Cl₅O₄ Oil 6 C₂₂H₂₁BrCl₄O₄Solid, 64-68° C. 7 C₂₃H₂₁Cl₄NO₄ Solid, 88-93° C. 9 C₂₅H₂₇Cl₄NO₆ Solid,106-110° C. 10 C₂₃H₂₅Cl₃O₄ Solid, 68-70° C. 11 C₂₃H₂₄Cl₄O₄ Oil 12C₂₃H₂₄Cl₄O₄ Liquid 13 C₂₃H₂₃Cl₅O₄ Liquid 14 C₂₃H₂₃Cl₅O₄ Oil 15C₂₃H₂₃Cl₅O₄ Liquid 16 C₂₃H₂₃Cl₅O₄ Solid, 56-60° C. 17 C₂₃H₂₃BrCl₄O₄Semi-solid 18 C₂₃H₂₃BrCl₄O₄ Liquid 19 C₂₃H₂₃Cl₄IO₄ Liquid 20C₂₄H₂₃Cl₄F₃O₄ Liquid 21 C₂₄H₂₃Cl₄NO₄ Solid, 89-95° C. 22 C₂₃H₂₃Cl₄NO₆Solid, 101-104° C. 23 C₂₄H₂₅Cl₄NO₆ Solid, 72-75° C. 24 C₂₃H₂₅Cl₄NO₄Liquid 25 C₂₅H₂₇Cl₄NO₅ Liquid 26 C₃₀H₂₉Cl₄NO₅ Liquid 27 C₂₆H₂₉Cl₄NO₆Liquid 28 C₂₉H₂₈Cl₄O₄ Liquid 29 C₂₃H₂₃Cl₄FO₄ Liquid 30 C₂₃H₂₄Cl₄O₅Liquid 31 C₂₆H₂₇Cl₆NO₃ Oil 32 C₂₅H₂₇Cl₄NO₄ Oil 33 C₂₁H₁₆Cl₄F₄O₄ Liquid34 C₂₅H₂₆Cl₄O₄S₂ Liquid 35 C₂₂H₂₀Cl₄O₅ Liquid 36 C₂₃H₂₂Cl₄O₅ Liquid 37C₂₃H₂₁Cl₅O₅ Liquid 38 C₂₃H₂₁Cl₅O₅ Liquid 39 C₂₃H₂₀Cl₆O₅ Oil 40C₂₄H₂₂Cl₆O₅ Oil 41 C₂₄H₂₆Cl₄O₄ Liquid 42 C₂₄H₂₅Cl₅O₄ Liquid 43C₂₄H₂₅BrCl₄O₄ Liquid 44 C₂₅H₂₅Cl₄F₃O₄ Liquid 45 C₂₄H₂₇Cl₄NO₃ Oil 46C₂₅H₂₉Cl₄NO₃ Oil 47 C₂₇H₃₁Cl₄NO₃ Oil 48 C₃₁H₃₃Cl₄NO₃ Oil 49 C₂₃H₂₄Cl₄O₅Oil 50 C₂₃H₂₃Cl₅O₅ Oil 51 C₂₅H₂₇Cl₅O₄ Oil 52 C₂₃H₂₃Cl₄NO₅ Oil 53C₂₃H₂₃Cl₄NO₅ Solid 54 C₂₃H₂₅Cl₅O₄ Oil

[0192] Surface-Treated Diet Test Against Tobacco Budworm

[0193] The compounds were evaluated for activity against the tobaccobudworm (Heliothis virescens [Fabricius]) in a surface-treated diettest.

[0194] In this test one mL of molten (65-70° C.) wheat germ-basedartificial diet was pipetted into each well of a four by six (24 well)multi-well plate (ID #430345-15.5 mm dia.×17.6 mm deep; Corning CostarCorp., One Alewife Center, Cambridge, Mass. 02140). The diet was allowedto cool to ambient temperature before treatment with candidateinsecticide.

[0195] For a determination of insecticidal activity, solutions of thecandidate insectides were prepared for testing using a Packard 204DTMultiprobe® Robotic System (Packard Instrument Company, 800 ResearchParkway, Meriden, Conn. 06450), in which the robot first diluted astandard 50 millimolar DMSO solution of candidate insecticide with a 1:1water/acetone solution (V/V) in a ratio of 1:7 stock solution towater/acetone. The robot subsequently pipetted 40 microliters of theso-prepared solution onto the surface of the diet in each of three wellsin the 24 multilate. The process was repeated with solutions of sevenother candidate insecticides. Once treated, the contents of themulti-well plate were allowed to dry, leaving 0.25 millimoles ofcandidate insecticide on the surface of the diet, or a concentration of0.25 millimolar. Appropriate untreated controls containing only DMSO onthe diet surface were also included in this test.

[0196] For evaluations of the insecticidal activity of a candidateinsecticide at varying rates of application, the test was established asdescribed above using sub-multiples of the standard 50 millimolar DMSOsolution of candidate insecticide. For example, the standard 50millimolar solution was diluted by the robot with DMSO to give 5, 0.5,0.05, 0.005, 0.0005 millimolar, or more dilute solutions of thecandidate insecticide. In these evaluations there were six replicates ofeach rate of application placed on the surface of the diet in the 24multi-well plate, for a total of four rates of application of candidateinsecticide in each plate.

[0197] In each well of the test plate was placed one second instartobacco budworm larvea, each weighing approximately five milligrams.After the larvae were placed in each well, the plate was sealed withclear polyfilm adhesive tape. The tape over each well was perforated toensure an adequate air supply. The plates were then held in a growthchamber at 25° C. and 60% relative humidity for five days (light 14hours/day).

[0198] After the five-day exposure period insecticidal activity for eachrate of application of candidate insecticide was assessed as percentinhibition of insect weight relative to the weight of insects fromuntreated controls, and percent mortality when compared to the totalnumber of insects infested.

[0199] Insecticidal activity data at selected rates of application fromthis test are provided in Table 3. The test compounds of formula I areidentified by numbers that correspond to those in Table 1. TABLE 3Insecticidal Activity of Certain (dihalopropenyl) phenylalkylsubstituted dihydrobenzofuran and dihydrobenzopyran derivativesDerivatives When Applied to the Surface of the Diet of Tobacco Budworm(Heliothis virescens [Fabricius]) Percent Percent Percent Growth Cmpd.Percent Growth Cmpd. No. Mortality Inhibition No. Mortality Inhibition 1100 100 2 100 100 3 100 100 4 100 100 5 100 100 6 100 100 7 100 100 9 078 10 100 100 11 100 100 12 100 100 13 100 100 14 100 100 15 100 100 16100 100 17 100 100 18 100 100 20 100 100 21 100 100 22 100 100 24 100100 25 100 100 27 100 100 28 100 100 29 100 100 30 100 100 31 100 100 32100 100 33 100 100 34 100 100 35 100 100 36 100 100 37 100 100 38 100100 39 100 100 40 100 100 41 100 100 42 100 100 43 100 100 44 100 100 45100 100 46 100 100 47 100 100 48 100 100 49 100 100 50 100 100 51 100100 52 100 100 53 100 100 54 100 100

[0200] As set forth in the foregoing Table 3, all of the compoundstested provided insecticidal activity, with nearly all providing 100%mortality and 100% growth inhibition of tobacco budworm.

[0201] For purposes of comparison, Compound 12 of the present inventionwas tested in side-by-side tests with certain analogous benzofuranylderived compounds wherein the test compounds were applied to the foliageof test plants. Compound 12 and the analogous compounds in these testshave the following structure:

[0202] where heterocycle is:

[0203] where y is 1: Position of Cmpd. Heterocycle No. D HeterocycleAttachment 12 O C 1 W O A 1 X O B 1 Y CH₂ A 6 Z O A 4

[0204] Compounds 12, W, X and Y were tested for insecticidal activity infoliar evaluations against tobacco budworm (Heliothis virescens[Fabricius]), cabbage looper (Trichoplusia ni [Hubner]) and DiamondbackMoth (Plutella xylostella) using the following methods:

[0205] Foliar Treated Test Against Tobacco Budworm and Cabbage Looper

[0206] Nine-to-ten day-old chick pea plants (Cicer arietinum) weresprayed at 15 psi to runoff on both upper and lower leaf surfaces withsolutions of test compound to provide application rates as high as 1000ppm of test chemical. The solvent used to prepare the solutions of testcompound was 10% acetone or methanol (v/v) and 0.1% of the surfactantoctylphenoxypolyethoxyethanol in distilled water. Four replicates, eachcontaining one chick pea plant, for each rate of application of testcompound were sprayed. The treated plants were transferred to a hoodwhere they were kept until the spray had dried.

[0207] The four chick pea plants for each replicate treated with testcompound as described above were removed from their pots by cutting thestems just above the soil line. The excised leaves and stems from thefour plants in each replicate were placed in individual 237 mL (8-ounce)paper cups, which contained a moistened filter paper. Five second-instar(7 days old) tobacco budworms or cabbage loopers (7 days old) werecounted into each cup, taking care not to cause injury. An opaqueplastic lid was placed on each cup, which was then held in a growthchamber for a 96 hour exposure period at 25° C., 50% relative humidityand photo-period of 12 hours light and 12 hours dark. At the end of the96 hour exposure period the cups were opened, and the numbers of dead,moribund, and live insects were counted. Using the insect counts, theefficacy of the test compound was expressed in percent control. Percentcontrol is derived from the total number of dead insects (TD) plus thetotal number of moribund insects (TM) as compared to the total number ofinsects (TI) in the test:${\% \quad {Control}} = {\frac{{TD} + {TM}}{TI} \times 100}$

[0208] The condition of the test plants was also observed forphytotoxicity and for reduction of feeding damage as compared to anuntreated control. Larvae are classified as “moribund” if they fail torapidly right themselves when turned over, but show movement, or if theyare severely reduced in size and do not appear to be feeding.

[0209] Results of these tests against tobacco budworm and cabbage looperare set forth below in Table 4.

[0210] Foliar Treated Test Against Diamondback Moth

[0211] Leaf discs 2.5 cm in diameter were cut from six-week-old cabbageleaves were dipped in solutions of test chemical of variousconcentrations to provide application rates as high as 1000 ppm of testcompound. The solvent used to prepare the solutions of test compound was10% acetone or methanol (v/v) and 0.1% of the surfactantoctylphenoxypolyethoxyethanol in distilled water. Four replicates, eachcontaining one cabbage leaf disc, for each rate of application of testcompound were dipped.

[0212] The four cabbage leaf discs for each replicate treated wereimmersed for five seconds in the solution of test compound as describedabove. Each discs was then placed in individual 50 mm Petrie dishescontaining a filter paper 42.5 mm in diameter that had been moistenedwith 100 μL of water. The uncovered Petrie dishes were then set asideuntil the leaf discs were dry. After this time, two third-instardiamondback moth larvae (10-14 days old) were carefully placed on eachleaf disc. A tight-fitting lid was then placed on each Petrie dish,which was which was then held in a growth chamber for a 96 hour exposureperiod at 25° C., 50% relative humidity and photo-period of 12 hourslight and 12 hours dark. At the end of the 96 hour exposure period thePetrie dishes were uncovered, and the numbers of dead, moribund, andlive insects were counted. Using the insect counts, the efficacy of thetest compound was expressed in percent control by methods set forthabove in tests against the tobacco budworm and cabbage looper.

[0213] Results of these tests against diamondback moth are set forthbelow in Table 4. TABLE 4 Insecticidal Activity Against Tobacco Budworm,Diamondback Moth and Cabbage Looper on Foliage Percent Control at a Rateof Application of 30 ppm Cmpd. ID TBW¹ DBM² CL³ Cmpd. 12 88 91 96 Cmpd.W 62 60 20 Cmpd. X 96 85 50 Cmpd. Y 5 Not tested Not tested Cmpd. Z 6060 20

[0214] Analysis of the results of the forgoing tests clearly indicatethat, although there is no significant difference between compound 12and compound X in control of tobacco budworm and diamondback moth,compound 12 is more active against cabbage looper than is compound X.Compound 12 is also more active against all three insect species thanare compounds W, Y and Z. Thus, when compared to certain analogousbenzofuranyl derived compounds, compound 12 of the present inventionprovides at least equal or unexpectedly better control of a broaderspectrum of insect species than does the aforementioned benzofuranderivatives.

[0215] Whole Plant Foliar Treated Test Against Cabbage Looper

[0216] For each rate of application of test compound, a 15 mL aliquot oftest solution was prepared. Sufficient test compound was dissolved in1.5 mL of acetone to provide an application rate as high as 1000grams/Ha. Each solution was then added to 13.5 mL of water containing300 ppm of a surfactant. There were four replicates for each rate ofapplication of test compound, and all tests included a known chemicalstandard as well as a standard of water and surfactant and untreatedchecks.

[0217] A maximum of 14 appropriately sized cabbage plants for each rateof application and replicate were arranged in a 28 pot plastic flat andsprayed with the 15 mL sample of test compound using an traveling boomsprayer equipped with a cone spray tip at a rate of 30 gallons/acreunder a pressure of 40-44 psi. The untreated checks were sprayed first,followed by the test compounds and standards, all in order of lowest tohighest rates of application. Once the spraying was complete, the testplants were allowed to air-dry on the conveyor on which they weresprayed.

[0218] For each rate of application and replication, sufficient Petriedishes, 50×9 mm in size, were lined with filter paper disks and eachwere moistened with 0.5 mL of distilled water. From each replicatecabbage plant at least three 2.5 cm disks were cut Each leaf disk wasthen placed in an individual Petrie dishes with the adaxial side of theleaf facing up. Following placement of the leaf disks, two neonatecabbage looper larvae were placed on each disk. Upon completion ofinfestation each Petrie dish was covered and held in a growth chamberfor a 96 hour exposure period at 25° C., 40%-60% relative humidity andphoto-period of 12 hours light and 12 hours dark. At the end of the 96hour exposure period the Petrie dishes were opened, and the numbers ofdead, moribund, and live insects were counted. Using the insect counts,the efficacy of the test compound was expressed in percent control.Percent control is derived from the total number of dead insects (TD)plus the total number of moribund insects (TM) as compared to the totalnumber of insects (TI) in the test:${\% \quad {Control}} = {\frac{{TD} + {TM}}{TI} \times 100}$

[0219] The condition of the test plants was also observed forphytotoxicity and for reduction of feeding damage as compared to anuntreated control. Larvae are classified as “moribund” if they fail torapidly right themselves when turned over, but show movement, or if theyare severely reduced in size and do not appear to be feeding. Results ofthese tests are set forth in Table 5 TABLE 5 Insecticidal ActivityAgainst Cabbage Looper on Foliage Percent Control at Indicted Rate ofApplication Cmpd. ID 100 g 50 g 25 g Cmpd. 12 100 100 88 Cmpd. X 13 8 8

[0220] These results clearly indicate that compound 12 is more activeagainst cabbage looper than is compound X.

[0221] Photostability

[0222] Again, for purposes of comparison, compound 12 of the presentinvention was tested in side-by-side tests with analogous benzofuranylderived compounds designated as compounds W, X, Y and Z as set forthabove to determine their photochemical stability, i.e., their rate ofphotolysis. These tests were conducted in the following manner:

[0223] For each compound tested, three glass microscope coverslips (12mm in diameter) for each illumination period (1, 3, 6, 12, and 24 hours)were spotted with 10 microliters of a one mg/mL acetonitrile or methanolsolution of test compound. Three coverslips were also spotted with testcompound and were not illuminated. The material on these non-illuminatedcoverslips was analyzed at the end of the experiment as described belowto determine the test compound stability on glass. The solvents in each10 microliter solution on each coverslip were allowed to evaporateleaving a thin film of test compound on each coverslip. Three of thecoverslips representing the zero hour illumination period were thenplaced in a 20 mL scintillation vial. In the vial was placed one mL ofacetonitrile, which extracted the test chemical from the coverslip. Thesolution was then transferred to a two-dram vial for analysis by HPLC.The average HPLC peak area generated by this sample defined the initiallevel of test compound. The remaining coverslips were then placed in thewater-cooled chamber of the exposure platform of a Suntest CPSilluminator (Heraeus Instruments GmbH; Bereich Original Hanau,Hersaeusstrasse R-14, Postfach 1563, D-6450 Hanau 1). The exposureplatform was covered with a quartz plate and maintained at about 25° C.for the duration of the test. The Suntest CPS illuminator employs afiltered xenon lamp, which provides illumination of a similar spectrumand intensity as sunlight. Three coverslips for each test compound wereremoved from the illuminator at 1, 3, 6, 12, and 24 hours of continuousillumination. Approximately eight hours of illumination is equivalent toone summer day at 40° N latitude. The three coverslips from each of theillumination periods were treated as described above and analyzed byHPLC. The average HPLC peak area from each of these illumination periodsrepresents a diminished amount of test compound when compared to theinitial level of test compound as determined from the zero hourillumination sample. The percents of test compound remaining from eachof these illumination periods were used to generate a degradation curvefrom which a half-life in hours was determined for each test compound.The relative half-lives for each compound compared to that of compound12 were then calculated as a percent of compound 12 half-life. Resultsof these tests are set forth in Table 6 below: TABLE 6 Photostability inHalf-life Hours Photolysis Percent of Cmpd. Half-life Compound 12 No(Hours) Half-life 12 19 100%  W 11 58% X 6 32% Y 4 21% Z 4 21%

[0224] Analyses of the results of the forgoing tests clearly indicatethat compound 12 is more photostable than any of the benzofuranylderivatives. Compound W, the most photostable benzofuranyl derivativetested, is only a little more than half (58%) as photostable as iscompound 12.

[0225] While this invention has been described with an emphasis uponpreferred embodiments, it will be understood by those of ordinary skillin the art that variations of the preferred embodiments may be used andthat it is intended that the invention may be practiced otherwise thanas specifically described herein. Accordingly, this invention includesall modifications encompassed within the spirit and scope of theinvention as defined by the following claims.

What is claimed is:
 1. A compound of formula I:

wherein R and R³ are independently selected from hydrogen, halogen,hydroxy, (C₁-C₃)alkyl, (C₃-C₆)cycloalkyl, (C₂-C₅)alkenyl,(C₂-C₅)alkynyl, halo(C₁-C₃)alkyl, (C₁-C₃)alkoxy, halo(C₁-C₃)alkoxy,(C₁-C₃)alkylthio, halo(C₁-C₃)alkylthio, (C₁-C₃)alkylsulfonyl,halo(C₁-C₃)alkylsulfonyl, cyano, nitro; optionally substituted aminowherein the optional substituent is selected from (C₁-C₄)alkyl,(C₁-C₃)alkylcarbonyl and (C₁-C₃)alkoxycarbonyl; optionally substitutedimidazolyl, optionally substituted imidazolinyl, optionally substitutedoxazolinyl, optionally substituted oxazolyl, optionally substitutedoxadiazolyl, optionally substituted thiazolyl, optionally substitutedpyrazolyl, optionally substituted triazolyl, optionally substitutedfuranyl, optionally substituted tetrahydrofuranyl, optionallysubstituted dioxolanyl, optionally substituted dioxanyl, —C(═J)—K, and—C(R¹²)—Q—R¹³, wherein the optional substituent is selected from(C₁-C₄)alkyl, halo(C₁-C₄)alkyl, (C₁-C₄)alkoxy,(C₁-C₄)alkoxy(C₁-C₄)alkyl, (C₃-C₆)cycloalkyl, (C₂-C₅)alkenyl,(C₂-C₅)alkynyl, cyano, nitro and aryl; where J is selected from O, S,NR¹⁴, and NOR¹⁴, where R¹⁴ is hydrogen, (C₁-C₄)alkyl, halo(C₁-C₄)alkyl,aryl and aryl(C₁-C₄)alkyl; K is selected from hydrogen, (C₁-C₃)alkyl,halo(C₁-C₃)alkyl, (C₁-C₃)alkoxy, (C₁-C₃)alkylamino anddi(C₁-C₃)alkylamino; Q is selected from O, S, and NR¹⁴, where R¹⁴ is aspreviously described; R¹² and R¹³ are independently selected fromhydrogen, (C₁-C₄)alkyl and halo(C₁-C₄)alkyl, and R¹² and R¹³ may betaken together with —T(CHR¹⁴)_(m)—, where m is an integer of 2 to 4; Tis selected from from O, S, and NR¹⁴, where R¹⁴ is as previouslydescribed; R¹ and R² are independently selected from hydrogen, halogenand (C₁-C₃)alkyl R⁴ is hydrogen; R⁵'s are independently selected fromhalogen; E is selected from CH₂, O, S and NR¹⁵ where R¹⁵ is selectedfrom hydrogen, (C₁-C₃)alkyl, (C₁-C₃)alkoxy(C₁-C₃)alkyl,aryl(C₁-C₃)alkyl, (C₂-C₄)alkenyl (C₁-C₃)alkyl, halo(C₂-C₄)alkenyl(C₁-C₃)alkyl, di(C₁-C₃)alkylphosphonate, formyl,(C₁-C₃)alkylcarbonyl, halo(C₁-C₃)alkylcarbonyl,(C₁-C₃)alkoxy(C₁-C₃)alkylcarbonyl, arylcarbonyl and(C₁-C₃)alkylsulfonyl; G is selected from O, S, CH₂O* and (CH₂)_(n) wherethe asterisk denotes attachment to E, and n is an integer selected from1, or 2, provided that E and G are not simultaneously O or S, x is aninteger selected from 0 or 1 and when x is 1, A is selected from O,S(O)_(p) and —NR¹⁵, where p is an integer selected from 0, 1 and 2, andR¹⁵ is as previously described; B is a bridging group,*—(CR¹⁶R¹⁷)_(q)—(CR¹⁸R¹⁹)_(r)—(CR²⁰R²¹)_(s)—L_(t)—(CR²²R²³)_(u)—(CR²⁴R²⁵)_(v)—(CR²⁶R²⁷)_(w)—,where the asterisk denotes attachment at A; q, r, s, u, v and w areintegers independently selected from 0, 1 and 2; and when q, r, s, u, vor w are 1 or 2, R¹⁶ through R²⁷, inclusively, are independentlyselected from hydrogen, (C₁-C₃)alkyl, halo(C₁-C₃)alkyl,(C₁-C₃)alkoxy(C₁-C₃)alkyl, and (C₃-C₆)cycloalkyl; t is an integerselected from 0 or 1; and when t is 1, L is selected from CH═CH; O,S(O)_(p); OS(O)₂, S(O)₂O, NR²⁸; N(oxide)R²⁸; NR²⁸SO₂; NR²⁸C(═O)NR²⁹;Si(CH₃)₂; C(═O), OC(═O), NHC(═O); ON═CH; HC═NO; C(═O)O; C(═O)NH;C(═NOR¹⁴) and [CR³⁰R³¹]_(z), where p is as previously described, R²⁸ andR²⁹ are independently selected from hydrogen, (C₁-C₃)alkyl,(C₁-C₃)alkylsulfonyl, (C₁-C₃)alkylcarbonyl, (C₂-C₅)alkenyl, and(C₂-C₅)alkynyl; z is an integer selected from 1 or 2; and R³⁰ and R³¹are independently selected from hydrogen and (C₁-C₃)alkyl; y is aninteger selected from 0 or 1; and when y is 1, D is selected from O;S(O)_(p); and NR¹⁴, where p and R¹⁵ are as previously described, whereinD is attached to the benzo-fused ring moiety set forth in formula I atany one of the positions designated 1-, 2-, 3- or 4-:

R⁶, R⁷, R⁸ and R⁹ are independently selected from hydrogen, halogen,(C₁-C₄)alkyl, (C₃-C₆)cycloalkyl, (C₂-C₅)alkenyl, (C₂-C₅)alkynyl,halo(C₁-C₄)alkyl, (C₁-C₄)alkoxy, halo(C₁-C₄)alkoxy, (C₁-C₄)alkylthio,halo(C₁-C₄)alkylthio, (C₁-C₄)alkylsulfonyl, halo(C₁-C₄)alkylsulfonyl,cyano, nitro, aryl, alkylcarbonylamino, arylcarbonylamino, and(C₁-C₄)alkoxycarbonylamino; R¹⁰ and R¹¹ are independently selected fromhydrogen, halogen, hydroxyl, alkyl, alkoxy, or R¹⁰ and R¹¹ takentogether are O forming a carbonyl group; OCH₂CH₂O or SCH₂CH₂S forming aketal or a thioketal group; or NOR¹⁵ forming an oxime, where R¹⁵ is aspreviously described; M is selected from *C(R³²R³³) and*C(R³²R³³)C(R³⁴R³⁵) where the asterisk indicates attachment to O andwherein R³² through R³⁵ are selected from hydrogen, halogen,(C₁-C₄)alkyl, (C₁-C₄)alkoxy(C₁-C₄)alkyl, and halo(C₁-C₄)alkyl, andagriculturally acceptable salts thereof.
 2. A compound of claim 1,wherein R and R³ are independently selected from halogen and(C₁-C₃)alkyl; R¹, R², and R⁴ are hydrogen; R⁵'s are independentlyselected from chlorine, bromine, and fluorine; E is O; G is (CH₂)_(n),where n is 1; x is 1, and A is O; and when q, r, s, u, v and w are 1 or2, R¹⁶ through R²⁷, inclusively, are hydrogen; t is 0 or 1, and when tis 1, L is selected from O, OC(═O), NHC(═O), ON═CH, and CH═NO; y is 1,and D is selected from O; S(O)_(p); and NR¹⁵, where p is 0, and R¹⁵ isselected from hydrogen, (C₁-C₃)alkyl, aryl(C₁-C₃)alkyl,(C₂-C₄)alkenyl(C₁-C₃)alkyl, and halo(C₂-C₄)alkenyl(C₁-C₃)alkyl, whereinD is attached to the benzo-fused moiety set forth in formula I at theposition designated 1 or 4; R⁶, R⁷, R⁸ and R⁹ are independently selectedfrom hydrogen, halogen, halo(C₁-C₄)alkyl and nitro; R¹⁰ and R¹¹ arehydrogen, or R¹⁰ and R¹¹ are taken together with O to form a carbonylgroup; and M is C(R³²R³³), where R³² and R³³ are independently(C₁-C₄)alkyl.
 3. A compound of formula II

wherein: R¹ and R² are hydrogen; R and R³ are selected from halogen and(C₁ to C₃) alkyl; R⁵ is halogen; R⁷, R⁸ and R⁹ are hydrogen, halogen,halo (C₁-C₄)alkyl or nitro; R¹⁰ and R¹¹ are hydrogen or taken togetherare ═O; B is (CH2)n where n is an integer from 2 to 6; and M isC(R³²R³³) where R³² and R³³ are halogen or (C₁-C₄)alkyl.
 4. A compoundof claim 3, wherein C³² and C³³ are C₁ to C₄ alkyl.
 5. A compound ofclaim 3, wherein C³² and C³³ are methyl.
 6. The compound:

namely,5-(3,3-dichloroprop-2-enyloxy)-2-[4-(2,2-dimethyl(2,3-dihydrobenzo[2,3-b]furan-7-yloxy))butoxy]-1,3-dichlorobenzene.7. A composition comprising an insecticidally effective amount of acompound of claim 1 and at least one agriculturally acceptable extenderor adjuvant.
 8. The insecticidal composition of claim 7, furthercomprising one or more second compounds selected from the groupconsisting of pesticides, plant growth regulators, fertilizers and soilconditioners.
 9. A method of controlling insects, comprising applying aninsecticidally effective amount of a composition of claim 7 to a locuswhere insects are present or are expected to be present.
 10. A method ofcontrolling insects, comprising applying an insecticidally effectiveamount of a composition of claim 8 to a locus where insects are presentor are expected to be present.